Article

Influence of roasting conditions on the biogenic amine content in cocoa beans of different Theobroma cacao cultivars

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Abstract

The objective of this study was to investigate how roasting process conditions affected the content of biogenic amines in cocoa beans of different Theobroma cacao varieties. The raw cocoa beans were roasted at four different temperatures (ranging from 110 °C to 150 °C) and three different air humidities (0.3% to 5.0%). Roasting process may significantly modify the profile and levels of biogenic amines. Tyramine was the most abundant amine in raw cocoa beans, followed by tryptamine and 2-phenylethylamine. Serotonin and dopamine were presented only in small amounts. However, it was found that roasted cocoa beans contained mainly 2-phenylethylamine, followed by tyramine, tryptamine, serotonin and dopamine. Parameters of roasting have a significant effect on the levels of each amine in all types of roasted beans. The highest amount of biogenic amines was observed in the samples roasted at the highest temperatures and in the air with increased humidity. In addition, the results revealed that the cacao cultivars significantly affect the levels of biogenic amines.

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... Nacional ("National") is a worldwide recognized cocoa variety produced in Ecuador and classified as "fine" grade, together with Criollo and Trinitario cocoas. It differs from other varieties by having a very short fermentation and yielding seeds of an excellent taste and aroma (Afoakwa et al., 2011(Afoakwa et al., , 2008Dand, 2011b;Kongor et al., 2016;Motamayor et al., 2008;Oracz and Nebesny, 2014). Nowadays, there are few materials of pure Nacional cocoa, being the predominant plantations natural hybrids between pure Nacional and Trinitario beans introduced from Venezuela and Trinidad. ...
... The upper limit values for these cocoas was higher than those obtained in this study. This variation between studies could rely on main factors affecting the phenolic content of cocoa beans, both intrinsic factors such as the genotype and extrinsic factors such as the harvest season and postharvest processes (fermentation and drying) (Afoakwa et al., 2011;Oracz and Nebesny, 2014;Wollgast and Anklam, 2000). ...
... It is known that geographical differences widely affect the cocoa beans TPC (Afoakwa et al., 2011;Oracz and Nebesny, 2014;Wollgast and Anklam, 2000). In this study, samples harvested in the Amazonian region cantons showed higher TPC than those obtained for Pacific Coast ones (between 42.75 ± 8.19 and 71.66 ± 3.94 mg GAE/g and between 33.55 ± 5.74 and 47.40 ± 6.20 mg GAE/g, respectively). ...
... Las AB pueden ser sintetizadas y degradadas de manera normal como resultado de la actividad metabólica en humanos, animales, plantas y microorganismos. Sin embargo, una ruta de producción muy común es vía descarboxilación de aminoácidos mediada por las aminodescarboxilasas de los microorganismos presentes en la fermentación (13) , en esos casos la cantidad total y variedad de AB, dependerá de la naturaleza de la proteína que predomina en el alimento y de los microorganismos que participan en la fermentación (11,14,15) . Las bacterias ácido lácticas (BAL) que participan frecuentemente en las fermentaciones de alimentos son ejemplo de esto, pues se han reportado bacterias específicamente del genero Lactobacillus tanto productoras (16,17) como degradadoras de AB (18)(19)(20) acción generada a través de enzimas amino oxidasas. ...
... En cacao se ha reportado que los tratamientos térmicos incrementan la cantidad de las AB (13) , por el contrario, en la E1 del presente estudio, el tratamiento térmico (tostado) parece provocar disminución de la concentración de AB en la mayoría de los casos (Tabla 3). Lo anterior también ha sido reportado que ocurre para algunas AB en muestras de soya fermentada (50) y puede atribuirse a la pirólisis de las AB promovida por altas temperaturas (150-240 °C) tal como se ha reportado previamente (51) . ...
... contenido total de AB durante el tostado, con la degradación de PUT, ESP, HIS y TIR. Se han identificado varias AB (2-FEN, TIR, TRIP, serotonina y dopamina) en semillas de cacao tostadas (13) y se ha reportado que estos compuestos dieron las concentraciones más altas cuando el tostado se realiza a temperaturas de 150 °C y contenido de humedad de 5.0 %, lo anterior coincide con lo reportado en la E2 el estudio actual, donde PUT e HIS siguieron presentes en la mayoría de los tratamientos posterior al tostado (150 °C), esto se puede atribuir a la descarboxilación de aminoácidos o por aminación y transaminación de las cetonas y aldehídos producidos durante las degradaciones de Strecker (13) . ...
Article
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Introducción. Las aminas biogénicas (AB) pueden encontrarse en alimentos sometidos a fermentación, en cantidades considerables pueden llegar a causar intoxicaciones al consumidor. Objetivo. Evaluar el efecto de la fermentación y el tostado sobre la producción-degradación de AB en semillas de cacao. Métodos. En una primera etapa (E1), bajo un diseño completamente al azar se verificó el papel de la fermentación sobre las AB mediante cuatro tratamientos, inhibición del crecimiento de levaduras; inhibición del crecimiento bacteriano; fermentación tradicional y semillas sin fermentar. En una segunda etapa (E2), con un diseño factorial 3X2 con medidas repetidas se evaluaron seis tratamientos, resultado de la combinación de dos bacterias ácido lácticas (BAL) (L. plantarum, L. fermentum, L. plantarum + L. fermentum) y dos concentraciones de cultivo iniciador (106 UFC/g, 108 UFC/g) para investigar el papel de BAL exógenas en la producción-supresión de AB. Resultados. En la E1 se comprobó la presencia de tres AB de interés, encontrándose putrescina en mayor cantidad (37 – 45,2 μg/g de semilla). Histamina y tiramina se encontraron en menores concentraciones sin efecto de la fermentación sobre la producción de AB. La E2 permitió observar un efecto de las BAL en la producción de putrescina, alcanzando valores hasta 41,1 μg/g cuando se inoculó la concentración más alta de BAL durante la fermentación. Histamina se redujo en las semillas después del tostado cuando se inoculó L. plantarum a 108 UFC/g. Conclusión. Las BAL exógenas no tienen un papel fundamental en la producción-degradación de AB durante la fermentación de semillas de cacao.
... A decrease of bioactive compounds, such as BAs and polyphenolic compounds, occurs in different steps of the cocoa beans processing, affecting their final content and functional properties in cocoa derivatives [10][11][12]. During roasting, physical and chemical changes occur in the beans, such as differences in colour, removal of undesirable volatile compounds, formation of desirable aroma and flavour, reduction of water content (up to 2%), and formation of a brittle structure, as well as changes in flavanols, proanthocyanidins and antioxidant activity [13,14]. ...
... In addition, peculiar cocoa volatile compounds are generated by Maillard reactions and their release is favoured by modifications of the matrix structure [15]. In spite of this, during roasting critical changes may also take place such as the formation of water-insoluble melanoidins, the degradation of catechin-containing compounds [16], the reduction of polyphenol content and antioxidant activity [17], and an increase of the biogenic amines content [12]. If some Maillard Reaction products, such as melanoidins, are required for the development of the peculiar cocoa sensory characteristics and brown colour, some furanic compounds are supposed to have negative effects on human health, as they can show cytotoxicity at high concentration and are "possibly carcinogenic to humans" [18]. ...
... To the best of our knowledge, there are no studies reporting the occurrence of CAD and HIS in raw cocoa beans, although there are few studies where BAs are identified in cocoa. Some authors [12] found tyramine, 2-phenylethylamine, tryptamine, serotonin, and dopamine in different varieties of raw cocoa beans; other authors [11] also found spermidine and spermine in Brazilian samples during fermentation. ...
Article
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The composition of microbiota and the content and pattern of bioactive compounds (biogenic amines, polyphenols, anthocyanins and flavanols), as well as pH, color, antioxidant and reducing properties were investigated in fermented Criollo cocoa beans and shells. The analyses were conducted after fermentation and drying (T1) and after two thermal roasting processes (T2, 120 °C for 22 min; T3, 135 °C for 15 min). The fermentation and drying practices affected the microbiota of beans and shells, explaining the great variability of biogenic amines (BAs) content. Enterobacteriaceae were counted in a few samples with average values of 103 colony forming units per gram (CFU g−1), mainly in the shell, while Lactobacillus spp. was observed in almost all the samples, with the highest count in the shell with average values of 104 CFU g−1. After T1, the total BAs content was found to be in a range of 4.9÷127.1 mg kg−1DFW; what was remarkable was the presence of cadaverine and histamine, which have not been reported previously in fermented cocoa beans. The total BAs content increased 60% after thermal treatment T2, and of 21% after processing at T3, with a strong correlation (p < 0.05) for histamine (ß = 0.75) and weakly correlated for spermidine (ß = 0.58), spermine (ß = 0.50), cadaverine (ß = 0.47) and serotonine (ß = 0.40). The roasting treatment of T3 caused serotonin degradation (average decrease of 93%) with respect to unroasted samples. However, BAs were detected in a non-alarming concentration (e.g., histamine: n.d ÷ 59.8 mg kg−1DFW; tyramine: n.d. ÷ 26.5 mg kg−1DFW). Change in BAs level was evaluated by principal component analysis. PC1 and PC2 explained 84.9% and 4.5% of data variance, respectively. Antioxidant and reducing properties, polyphenol content and BAs negatively influenced PC1 with both polyphenols and BA increasing during roasting, whereas PC1 was positively influenced by anthocyanins, catechin and epicatechin.
... It was found that yeasts, filamentous fungi, lactic and acetic acid bacteria as well as members of the genus Bacillus, are typically present, all of them being able to produce BAs [43]. As a consequence of the protection mechanism of bacteria against the acid medium, decarboxylase activity is favored by low pH values during fermentation [44]. Moreover, contaminating bacteria can also decarboxylate amino acids to support a further accumulation of BAs. ...
... On the contrary, considering samples of the same geographical origin, Oracz and Nebesny (2014) reported for raw cocoa beans from Ecuador and Indonesia, much lower total BAs content, not exceeding 5.0 and 6.0 mg kg −1 , respectively. However, only five BAs were considered in this study, neglecting natural polyamines PUT, SPM, and SPD, as well as, HIS and CAD, representing in our study the most abundant compounds [44]. ...
... Guillen-Casla et al. (2012) [20] reported that TYR, PHE, serotonin, and HIS were the main amines in cocoa beans, although also PUT, dopamine, and ethanolamine have also been determined. Comparison among samples of same geographical origin (samples 1 and 7), displayed comparable (Ecuador) or higher (Indonesia) amounts of PHE, while our samples always showed much higher concentration of TYR for both raw cocoa beans [44]. In addition, do Carmo Brito et al. (2017) [5] found different results. ...
Article
Full-text available
Biogenic amines (BAs), polyphenols, and aroma compounds were determined by chromatographic techniques in cocoa beans of different geographical origin, also considering the effect of roasting (95, 110, and 125 °C). In all samples, methylxantines (2.22–12.3 mg kg−1) were the most abundant followed by procyanidins (0.69–9.39 mg kg−1) and epicatechin (0.16–3.12 mg kg−1), all reduced by heat treatments. Volatile organic compounds and BAs showed variable levels and distributions. Although showing the highest BAs total content (28.8 mg kg−1), Criollo variety presented a good aroma profile, suggesting a possible processing without roasting. Heat treatments influenced the aroma compounds especially for Nicaragua sample, increasing more than two-fold desirable aldehydes and pyrazines formed during the Maillard cascade and the Strecker degradation. As the temperature increased, the concentration of BAs already present in raw samples increased as well, although never reaching hazardous levels.
... Also tea, coffee, and cocoa, as well as their derivatives, have been considered as a source of BAs, although few studies are present in the literature, mainly regarding raw materials ( Cirilo et al., 2003;Casal et al., 2004;Vasconcelos et al., 2007;Palavan-Unsal et al., 2007;Oracz and Nebesny, 2014). Profiles and concentrations are reported to be very much varied as these molecules can be formed/accumulated in relation with the type and quality of raw materials, their origin and processing which in turn is driven by manufacturing technology, agronomic conditions, trading, blend, storage, and distribution of these commodities ( Dias et al., 2012;Zhang et al., 2014;Restuccia et al., 2016;CarmoBrito et al., 2017). ...
... In this way, UHPLC allows excellent separations in shorter analysis time compared to those obtained by conventional LC. However, the direct separation of BAs is difficult in reversed-phase mode so that precolumn derivatization has usually been performed in UHPLC methods (Oracz and Nebesny, 2014). Finally, LC-ELSD methodology showed accurate and precise determination of up to eight BAs in organic and fair trade cocoa-based products without the need of the derivatization step with time saving and with good values of recovery and precision ( Restuccia et al., 2016;Spizzirri et al., 2016a,b). ...
... This pointed out a new "thermogenic" BAs formation. This effect was recently underlined during cocoa beans roasting (Oracz and Nebesny, 2014), although the temperatures involved (110-150°C) were quite different from those applied during coffee thermal treatment. Strecker degradation seems to be responsible for the formation of BAs by thermal decarboxylation of amino acids in the presence of α-dicarbonyl compounds formed during the Maillard reaction ( Granvogl et al., 2006) or lipid peroxidation products . ...
... Also tea, coffee, and cocoa, as well as their derivatives, have been considered as a source of BAs, although few studies are present in the literature, mainly regarding raw materials (Cirilo et al., 2003;Casal et al., 2004;Vasconcelos et al., 2007;Palavan-Unsal et al., 2007;Oracz and Nebesny, 2014). Profiles and concentrations are reported to be very much varied as these molecules can be formed/accumulated in relation with the type and quality of raw materials, their origin and processing which in turn is driven by manufacturing technology, agronomic conditions, trading, blend, storage, and distribution of these commodities (Dias et al., 2012;Zhang et al., 2014;Restuccia et al., 2016;CarmoBrito et al., 2017). ...
... In this way, UHPLC allows excellent separations in shorter analysis time compared to those obtained by conventional LC. However, the direct separation of BAs is difficult in reversed-phase mode so that precolumn derivatization has usually been performed in UHPLC methods (Oracz and Nebesny, 2014). Finally, LC-ELSD methodology showed accurate and precise determination of up to eight BAs in organic and fair trade cocoa-based products without the need of the derivatization step with time saving and with good values of recovery and precision Spizzirri et al., 2016a,b). ...
... This pointed out a new "thermogenic" BAs formation. This effect was recently underlined during cocoa beans roasting (Oracz and Nebesny, 2014), although the temperatures involved (110-150°C) were quite different from those applied during coffee thermal treatment. Strecker degradation seems to be responsible for the formation of BAs by thermal decarboxylation of amino acids in the presence of α-dicarbonyl compounds formed during the Maillard reaction (Granvogl et al., 2006) or lipid peroxidation products . ...
... Salsolinol and biogenic amines are minor alkaloids that do not affect the cocoa flavor, whereas they may contribute to the psychopharmacological activity (Tuenter et al., 2018). However, consumption of those compounds in high concentration may cause undesirable physiological and/or toxicological problems (Aprotosoaie et al., 2016;Oracz & Nebesny, 2014). The levels of the biogenic amines mainly depend on the thermal bean processing, such as roasting (Oracz & Nebesny, 2014), whereas there is no information regarding the impact of alkalization. ...
... However, consumption of those compounds in high concentration may cause undesirable physiological and/or toxicological problems (Aprotosoaie et al., 2016;Oracz & Nebesny, 2014). The levels of the biogenic amines mainly depend on the thermal bean processing, such as roasting (Oracz & Nebesny, 2014), whereas there is no information regarding the impact of alkalization. ...
Article
Alkalization is a process to improve color, dispersibility and flavor of cocoa powder but is likely to have a negative effect on the phytochemicals. Hereto, the impact of alkalization degree (none, medium and high) on the potential mood-enhancing compounds corresponding to the four levels of the mood pyramid model (flavanols, methylxanthines, biogenic amines and orosensory properties) was investigated. The phytochemical content, analyzed via UPLC-HRMS, showed reduction of specific potential mood-enhancing compounds upon alkalization, implying a decrease in bitterness and astringency. Moreover, volatile compounds analysis via HS-SPME-GC-MS indicated that alkalization reduced the levels of volatile compounds, responsible for acidity, fruity, floral and cocoa aromas. With respect to the orosensory properties, the cocoa powder palatability was suggested to be increased due to reduced acidity, bitterness, and astringency, while the desired volatile compounds were reduced. However, sensorial analysis is required to link the volatile results with the overall effect on the flavor perception.
... In addition, naturally occurring microorganisms such as yeasts, filamentous fungi, LAB and AAB, are able to hydrolyze the proteins present in cocoa beans, thus providing FAA to the BA synthesis [10] or the production of fusel alcohols, acids and esters. Although many factors influence decarboxylase activity, this is amplified at low pH values, as a protection mechanism of bacteria against the acid medium [11]. In general, LAB is the most important biogenic amine producers in fermented foods [9], in spite of other less studied microorganisms like Enterobacteriaceae, Pseudomonads, Clostridium perfringens and yeasts. ...
... Sample preparation was performed according to the methods reported by [11] with slight modifications. Briefly, one gram of sample was defatted through three successive washes with 5 mL of hexane (3 × 5 mL), and then defatted samples were dried under nitrogen. ...
Article
Full-text available
Yeast starters for cocoa fermentation are usually tested according to their enzymatic activities in terms of mucilage degradation and flavor improvement, disregarding their influence on the production or elimination of toxic compounds as biogenic amines (BAs), important for human health. In this work, we tested 145 strains belonging to 12 different yeast species and isolated from the Colombian fermented cocoa beans (CB) for their capability of producing BAs in vitro. Sixty-five strains were able to decarboxylate at least one of the amino acids tested. Pichia kudriavzevii ECA33 (Pk) and Saccharomyces cerevisiae 4 (Sc) were selected to evaluate their potential to modulate BAs, organic acids, and volatile organic compounds (VOCs) accumulation during a simulated cocoa fermentation. The growth of Sc or Pk in the presence of CB caused a significant reduction (p < 0.05) of 2-phenylethylamine (84% and 37%) and cadaverine (58% and 51%), and a significant increase of tryptamine and putrescine with a strong influence of temperature in BA formation and degradation. In addition, our findings pointed out that Pk induced a major production of fatty acid- and amino acid-derived VOCs, while Sc induced more VOCs derived from fatty acids metabolism. Our results suggest the importance of considering BA production in the choice of yeast starters for cocoa fermentation.
... Free tryptophan (which can be present as protein-bound as well), is transformed during fermentation into biogenic amines (5-hydroxytryptamine and tryptamine) [9]. Although the exact mechanism of tryptamine formation in cocoa beans has not been revealed, Oracz and Nebesny [14] proposed a mechanism of its enzymatic formation from tryptophan ( Figure 1) and do Carmo Brito et al. [15] reported that the level of tryptamine decreases in the first four days of fermentation, only to slowly increase to virtually the same level by the sixth day. The presence of small amounts of tryptamine in raw cocoa beans has also been reported, as well as differences regarding variety (due to different composition of the bean) and origin (due to differences in cultivation conditions and microflora involved in the fermentation process) of cocoa beans [14]. ...
... Although the exact mechanism of tryptamine formation in cocoa beans has not been revealed, Oracz and Nebesny [14] proposed a mechanism of its enzymatic formation from tryptophan ( Figure 1) and do Carmo Brito et al. [15] reported that the level of tryptamine decreases in the first four days of fermentation, only to slowly increase to virtually the same level by the sixth day. The presence of small amounts of tryptamine in raw cocoa beans has also been reported, as well as differences regarding variety (due to different composition of the bean) and origin (due to differences in cultivation conditions and microflora involved in the fermentation process) of cocoa beans [14]. Therefore, it is yet to be revealed whether the process of tryptamine synthesis from tryptophan is spontaneous, or whether endogenous enzymes or enzymes of microflora during fermentation are involved. ...
Article
Full-text available
Chocolate production is a complex process during which numerous chemical reactions occur. The most important processes, involving most of the reactions important for development of the proper chocolate flavor, are fermentation, drying and roasting of cocoa bean, and chocolate conching. During fermentation, formation of important precursors occurs, which are essential for further chemical reactions in the following processes of chocolate production. Roasting is one of the most important processes due to the occurrence of Maillard’s reactions, during which aroma compounds are formed. In this paper, we have reviewed the most important chemical reactions that occur with proteins, carbohydrates, lipids, and polyphenols. Additionally, we present other components that may be naturally present or form during the production process, such as methylxanthines, aldehydes, esters, ketones, pyrazines, acids, and alcohols.
... mg/kg) were detected in P. kudriavzevii treatments (Pk and ScPk), suggesting that this yeast can be associated with the buildup of this amine. Furthermore, phenylethylamine can be formed during cocoa dehydration, due to release from conjugated amines or to the oxidative decarboxylation of the precursor amino acid (phenylalanine) at high temperatures (Oracz & Nebesny, 2014). Phenylethylamine is an important hypothalamic stimulating amine and, thus, can induce feelings of well-being and affect the levels of serotonin and brain endorphins, improving mood (Afoakwa, 2008). ...
... Phenylethylamine is an important hypothalamic stimulating amine and, thus, can induce feelings of well-being and affect the levels of serotonin and brain endorphins, improving mood (Afoakwa, 2008). But at high levels (≥30 mg/kg), this amine can be detrimental to human health, inducing migraines (Oracz & Nebesny, 2014;Jeon, Lee, & Mah, 2018). The levels of phenylethylamine obtained with the different treatments are far below the values capable of causing adverse effect to human health. ...
Article
The use of starters during fermentation has been gaining momentum as it can warrant high-quality chocolate. The objective of this study was to investigate the influence of Saccharomyces cerevisiae (Sc) and Pichia kudriavzevii (Pk) during on-farm fermentation on physico-chemical and microbiological characteristics and levels of methylxanthines and bioactive amines of cocoa. Four treatments were used: ScPk (1:1), only Sc, only Pk, and no starter (control). The starters lead to changes throughout fermentation, but provided fermented cocoa with similar pH, titratable acidity, reducing sugars and phenolic compounds. ScPk shortened fermentation time by 24 h. The ScPk fermented and dried cocoa had higher levels of monomeric phenols, methylxanthines, phenylethylamine and lower levels of the putrefactive amines – putrescine and cadaverine (p<0.05). The results were confirmed by multivariate analysis. Based on these results, the mixture of both yeasts species is a promising starter for cocoa fermentation decreasing duration time and modulating high-quality components.
... Cocoa beans also contain a further interesting group of compounds arising from the enzymatic and/or (chemical) decarboxylation of amino acids representing bioactive amines, where mainly 2-phenylethylamine, tyramine, tryptamine, serotonin and dopamine are found [118][119][120]. Cocoa can also be a source of polyamines (spermidine and spermine), which may also contribute to cocoa's antioxidant activity [118]. ...
... The changes in bioactive amines may be partly attributed through amino acid decarboxylation by microbial enzymes during the fermentation process of cocoa beans and their fate has been discussed in [118]. The roasting process also modifies significantly the profile and levels of biogenic amines [120]. ...
Article
Full-text available
The protein fractions of cocoa have been implicated influencing both the bioactive potential and sensory properties of cocoa and cocoa products. The objective of the present review is to show the impact of different stages of cultivation and processing with regard to the changes induced in the protein fractions. Special focus has been laid on the major seed storage proteins throughout the different stages of processing. The study starts with classical introduction of the extraction and the characterization methods used, while addressing classification approaches of cocoa proteins evolved during the timeline. The changes in protein composition during ripening and maturation of cocoa seeds, together with the possible modifications during the post-harvest processing (fermentation, drying, and roasting), have been documented. Finally, the bioactive potential arising directly or indirectly from cocoa proteins has been elucidated. The “state of the art” suggests that exploration of other potentially bioactive components in cocoa needs to be undertaken, while considering the complexity of reaction products occurring during the roasting phase of the post-harvest processing. Finally, the utilization of partially processed cocoa beans (e.g., fermented, conciliatory thermal treatment) can be recommended, providing a large reservoir of bioactive potentials arising from the protein components that could be instrumented in functionalizing foods.
... there can be decreases on total, spermidine, tryptamine, tyramine and serotonin contents, and the production and accumulation of 2-phenylethylamine (Gloria, Deus, & Franca, 2019). During cocoa roasting, there can be lipid oxidation, Maillard reaction and thermal decarboxylation of amino acids with formation of amines, including 2-phenylethylamine (Oracz & Nebesny, 2014), spermine (Delgado-Ospina et al., 2020) and tryptamine (Oracz & Nebesny, 2014). However, there can also be degradation of some bioactive amines, e.g. ...
... there can be decreases on total, spermidine, tryptamine, tyramine and serotonin contents, and the production and accumulation of 2-phenylethylamine (Gloria, Deus, & Franca, 2019). During cocoa roasting, there can be lipid oxidation, Maillard reaction and thermal decarboxylation of amino acids with formation of amines, including 2-phenylethylamine (Oracz & Nebesny, 2014), spermine (Delgado-Ospina et al., 2020) and tryptamine (Oracz & Nebesny, 2014). However, there can also be degradation of some bioactive amines, e.g. ...
Article
Chocolate is an important source of free bioactive amines and amino acids which play important roles in human health. Considering the limited information on the bioaccessibility of these compounds from chocolate, the objective of this study was to characterize their profiles and bioaccessibility in 70% cocoa dark chocolate through in vitro simulation of oral, gastric and intestinal digestions. Seven amines were detected; polyamines were predominant before in vitro digestion, whereas tyramine, cadaverine and spermidine after digestion. All amines showed high bioaccessibility with slight influence of digestive enzymes. Amines increased after gastrointestinal digestion: tyramine (13-fold), tryptamine (9-fold), others (2.4–4.2-fold) and histamine appeared. All amino acids, GABA and ammonia were detected in chocolate, and their contents increased after in vitro digestion due to digestive enzymes (4.6, 2.8 and 2.1, respectively). Dark chocolate protein is a good source of tryptophan, phenylalanine + tyrosine, isoleucine, histidine, but limiting for lysine, leucine, and threonine. https://doi.org/10.1016/j.foodchem.2020.128397 Anyone clicking on this link before February 16, 2021 will be taken directly to the final version of your article on ScienceDirect, which they are welcome to read or download: https://www.sciencedirect.com/science/article/pii/S0308814620322597
... Increased roasting time or temperature of a roasting treatment resulted in a decreased levels of these molecules, as expected from previous research (Pinto & Chichester, 1966). Both L-tyrosine and L-α-phenylalanine diminished with more than 80% when applying a roasting treatment at 160°C for 30 min, compared to the non-roasted sample ( (Oracz & Nebesny, 2014). A diminution of 5-hydroxy-dL-tryptophan (5-HTP) during roasting could be expected, as this compound can degrade to serotonin after thermal decarboxylation; moreover, it is sensitive to oxidation (Martins & Gloria, 2010). ...
... With regard to the amino acids (L-tryptophan, L-tyrosine, L-α-phenylalanine) and biogenic amines (tryptamine, tyramine, 2-phenylethylamine and salsolinol), no signi cant di erences (p > 0.05) were found either, except for serotonin, which was more abundant in the CR chocolate, compared to the MR2 chocolate. One type of reaction which can occur during roasting is the decarboxylation of amino acids, resulting in formation of the corresponding biogenic amines (Oracz & Nebesny, 2014). Since the levels of amino acids and biogenic amines in general did not di er signi cantly, the CR and MR had a comparable impact on these compounds and decarboxyla-5.3. ...
Book
Roasting plays a critical role in the production process of cocoa liquor and chocolate. Besides desirable changes in color and moisture content, flavor development is one of the most important reasons to roast cocoa. By means of a convective and/or conductive heat transfer, cocoa and nutty flavors are generated within the roasted beans, while the bitter taste and astringent mouthfeel are reduced. Roasting via a convective and/or conductive heat transfer is easy applicable and therefore also commonly used. However, these roasting techniques are lately questioned due to the long roasting times needed to sufficiently heat the core of the beans. Therefore, a growing interest is encountered to search for optimal roasting conditions and/or alternative roasting techniques, with the development of a desirable flavor profile as primary criterion. Within this research a comparison was made between conventional and microwave-assisted roasting with the main focus on flavor. The impact of varying roasting conditions (i.e. time, temperature and power input) on the flavor profile of cocoa liquor and chocolate was investigated via both instrumental (i.e. HS-SPME-GC-MS, UPLC-HRMS) and sensory (i.e. trained panel, consumer panel) techniques. Results confirmed that microwave-assisted roasting has the potential to be used as alternative technique.
... Cocoa beans also contain a further interesting group of compounds arising from the enzymatic and/or (chemical) decarboxylation of amino acids representing bioactive amines, where mainly 2-phenylethylamine, tyramine, tryptamine, serotonin and dopamine are found [118][119][120]. Cocoa can also be a source of polyamines (spermidine and spermine), which may also contribute to cocoa's antioxidant activity [118]. ...
... The changes in bioactive amines may be partly attributed through amino acid decarboxylation by microbial enzymes during the fermentation process of cocoa beans and their fate has been discussed in [118]. The roasting process also modifies significantly the profile and levels of biogenic amines [120]. ...
Article
The protein fractions of cocoa have been implicated influencing both the bioactive potential and sensory properties of cocoa and cocoa products. The objective of the present review is to show the impact of different stages of cultivation and processing with regard to the changes induced in the protein fractions. Special focus has been laid on the major seed storage proteins throughout the different stages of processing. The study starts with classical introduction of the extraction and the characterization methods used, while addressing classification approaches of cocoa proteins evolved during the timeline. The changes in protein composition during ripening and maturation of cocoa seeds, together with the possible modifications during the post-harvest processing (fermentation, drying, and roasting), have been documented. Finally, the bioactive potential arising directly or indirectly from cocoa proteins has been elucidated. The “state of the art” suggests that exploration of other potentially bioactive components in cocoa needs to be undertaken, while considering the complexity of reaction products occurring during the roasting phase of the post-harvest processing. Finally, the utilization of partially processed cocoa beans (e.g., fermented, conciliatory thermal treatment) can be recommended, providing a large reservoir of bioactive potentials arising from the protein components that could be instrumented in functionalizing foods.
... In addition, factors such as temperature, fermentation strain and mode, free amino acid content, salt concentration, and pH can also affect the synthesis of BAs in foods [13][14][15]. Oracz and Nebesny indicated that the content of BAs in cocoa beans increases with the increasing roasting temperature (110 • C to 150 • C) and air humidity (0.3% to 5.0%) [16]. Therefore, inhibiting the formation of BAs in foods by reducing free amino acid contents, limiting the growth of amine-positive microorganisms, and changing food processing conditions and additives has become a research focus [17,18]. ...
... The results of BA detection showed that the contents of ETM, PEM, and HIM in green tea reached 516.07 µg/g, 25.85 µg/g, and 73.22 µg/g, increased by 656.4%, 211.1%, and 164.2% compared with those of the original leaves, respectively ( Figure 2 and Table S1). Similarly, previous studies have also shown that the levels of BAs such as PEM, HIM, and TYM in coffee and cocoa beans would significantly increase after hightemperature treatment [16,38]. Meanwhile, two new BAs, PYN (47.03 µg/g) and PTN (36.14 µg/g), were synthesized in the process of producing green tea. ...
Article
This study aimed to evaluate the effects of processing methods on the content of biogenic amines in Zijuan tea by using derivatization and hot trichloroacetic acid extraction with HPLC-UV. The results showed that the most abundant biogenic amine in the original leaves was butylamine, followed by ethylamine, methylamine, 1,7-diaminoheptane, histamine, tyramine, and 2-phenethylamine. However, during the process of producing green tea, white tea, and black tea, the content of ethylamine increased sharply, which directly led to their total contents of biogenic amines increasing by 184.4%, 169.3%, and 178.7% compared with that of the original leaves, respectively. Unexpectedly, the contents of methylamine, ethylamine, butylamine, and tyramine in dark tea were significantly reduced compared with those of the original leaves. Accordingly, the total content of biogenic amines in dark tea was only 161.19 μg/g, a reduction of 47.2% compared with that of the original leaves, indicating that the pile-fermentation process could significantly degrade the biogenic amines present in dark tea.
... During roasting non-volatile compounds that do not participate on cacao flavor development are also produced. Some of these compounds are biogenic amines such as 2-phenylethylamine, tyramine, tryptamine, serotonin, and dopamine, which have a vital role in the mood-enhancing effect cacao (Aprotosoaie et al., 2016;Oracz & Nebesny, 2014). ...
... Roasting is one of the important steps which affects the quality characteristic of cocoa bean during industrial processing (Oracz and Nebesny, 2014). ...
Article
Flavour is important factor and central to acceptability of cocoa products such as chocolate and contributes to determining the quality. The quality of chocolate flavour is influence by several variable factors since in the stage of post-harvest treatments and handling till in manufacturing process. The aim of this paper was review and discuss all relevant studies in relation to cocoa beans and chocolate production, and identify their influence of processing techniques on flavour and characteristics of the cocoa processed products. This information hopefully has potential benefits on the making process of a chocolate manufacture.Keywords: cocoa, processing technique, flavour, characteristic, chocolate.ABSTRAK. Citarasa merupakan salah satu faktor penting dan sebagai salah satu pusat penerimaan produk olahan kakao seperti cokelat dan berkontribusi dalam penetapan mutu. Mutu citarasa produk cokelat dipengaruhi oleh beberapa variabel faktor, sejak pada tahap penanganan pasca-panen hingga tahap proses pengolahan di pabrik. Tulisan ini disajikan bertujuan untuk mengulas dan membahas serta mendiskusikan semua hasil studi yang pernah dilakukan, yang berhubungan dengan biji kakao dan produksi cokelat serta mengidentifikasi pengaruh cara pengolahannya terhadap citarasa dan karaketeristik produk olahan kakao. Informasi ini diharapkan mempunyai potensi yang bermanfaat pada proses pengolahan kakao di pabrik cokelat.Kata kunci : kakao, cara pengolahan, citarasa, karakteristik, cokelat.
... Knowledge of the phenomena that modulate the biochemical reactions that occur during the transformation of cocoa seeds is necessary to establish a control over this bioprocess, based on its proper management to produce cocoa with desired quality characteristics . In this sense, some authors have studied this bioprocess under laboratory conditions to generate a knowledge base as a guide to elucidate the dynamics of flavor formation during cocoa transformation from seeds to beans (John et al. 2016;Eyamo Evina et al. 2016;Kadow et al. 2015;Oracz and Nebesny 2014;Yaw 2014;Amin, Jinap, and Jamilah 1998;Voigt and Biehl 1995;Biehl et al. 1985). These studies are of great relevance for being pioneers in developing methodologies that allow carrying out the cocoa transformation of seeds in a controlled manner. ...
Article
Full-text available
Chocolate is a widely consumed product worldwide due to its exquisite flavor, which comes from the unique and fascinating cocoa flavor. This flavor depends on little controllable variables such as the genotype and the agroecological niche, and on the other side, on postharvest operations: (1) cocoa transformation from seeds to beans that comprises cocoa seeds preconditioning, fermentation , and drying, and (2) the production of chocolate from the bean in which roasting is highlighted. Postharvest transformation operations are critically important because during these, cocoa flavor is formed, allowing the differentiation of two categories: bulk and specialty cocoa. In this sense, this article presents an overview of cocoa postharvest operations, the variables and phenomena that influence and control the physical and biochemical transformation from seeds to cocoa beans, and their relation to the formation of chocolate flavor. Moreover, research perspectives in terms of control and management of postharvest practices in order to obtain cocoa with differentiated and specialty characteristics "from bean to bar" are discussed.
... Knowledge of the phenomena that modulate the biochemical reactions that occur during the transformation of cocoa seeds is necessary to establish a control over this bioprocess, based on its proper management to produce cocoa with desired quality characteristics . In this sense, some authors have studied this bioprocess under laboratory conditions to generate a knowledge base as a guide to elucidate the dynamics of flavor formation during cocoa transformation from seeds to beans (John et al. 2016;Eyamo Evina et al. 2016;Kadow et al. 2015;Oracz and Nebesny 2014;Yaw 2014;Amin, Jinap, and Jamilah 1998;Voigt and Biehl 1995;Biehl et al. 1985). These studies are of great relevance for being pioneers in developing methodologies that allow carrying out the cocoa transformation of seeds in a controlled manner. ...
Article
Chocolate is a widely consumed product worldwide due to its exquisite flavor, which comes from the unique and fascinating cocoa flavor. This flavor depends on little controllable variables such as the genotype and the agroecological niche, and on the other side, on postharvest operations: (1) cocoa transformation from seeds to beans that comprises cocoa seeds preconditioning, fermentation, and drying, and (2) the production of chocolate from the bean in which roasting is highlighted. Postharvest transformation operations are critically important because during these, cocoa flavor is formed, allowing the differentiation of two categories: bulk and specialty cocoa. In this sense, this article presents an overview of cocoa postharvest operations, the variables and phenomena that influence and control the physical and biochemical transformation from seeds to cocoa beans, and their relation to the formation of chocolate flavor. Moreover, research perspectives in terms of control and management of postharvest practices in order to obtain cocoa with differentiated and specialty characteristics “from bean to bar” are discussed.
... Anthocyanins area practical indicator for producers because they allow them to follow the evolution of fermentation in a visual way. In raw cocoas, the content of this type of polyphenols can increase as the intensity of solar radiation increases and in the absence of irrigation during the development of the fruit, as part of a protection mechanism (Beer, 1987;Oracz and Nebesny, 2014). Bajo Cauca is the zone with less rainfall frequency in relation to Uraba and Magdalena Medio, which could induce an oxidative stress in the productive units that did not have an irrigation system, thus generating a higher ratio of anthocyanins (2.12 AE 0.15). ...
Article
Full-text available
The aim of this study was to compare the quality of a mixture of cocoa harvested and fermented in three subregions of Antioquia (Colombia), from the chemometric profile based on multivariate statistical analysis. A mixture of clones CCN-52, ICS-1, FLE-2, and FEC-2 harvested in Bajo Cauca, Uraba and Magdalena Medio were subjected to a spontaneous fermentation. The characterization of raw and well-fermented cocoa was performed through 38 parameters, and results were compared by a Principal Component Analysis (PCA) and a Cluster Analysis (CA), followed by a Principal Factors Analysis (PFA- CA). The CA showed that there are differences among subregions only in raw cocoa from Bajo Cauca. PCA allowed identifying the variability between raw and fermented cocoa in a representative way and these results were consistent with the chemical profile. Besides, the number of parameters to differentiate raw cocoa from different subregions was reduced (11–13 parameters) and it was possible to characterize well fermented cocoa with only 10 parameters of 38. PFA-CA consolidated in three factors a grouping to identify the cocoa quality according to the process or interest of the sensory or functional properties. Factor 1 (cocoa quality indicators with functional properties), Factor 2 (indicators of quality of the beginning of fermentation) and Factor 3 (indicators of quality of well-fermented cocoa) each one with a weight of 39, 35 and 26 respectively.
... During roasting, temperatures of 110-160°C are employed (Farah, Zaibunnisa, & Misnawi, 2012). This process plays an essential role in the development of the typical flavor of chocolate, such as a more intense brown color and textural changes (Oliviero, Capuano, Cämmerer, & Fogliano, 2009;Oracz & Nebesny, 2014). The roasted beans are broken into fragments called nibs which are ground to form a mass or liquor (Fig. 2B) (Copetti, 2009;Wood, 1985). ...
... These reactions allow new compounds to form, which contributes to the characteristic aroma, taste and colour of chocolate [23,24]. Oracz, et al. [25] stated that during the roasting process, conditions such as time and temperature influence phenolic stability, as well as the characteristics of the obtained taste. ...
Article
Full-text available
The polyphenol content of cocoa beans and the products derived from them, depend on the regions in which they are grown and the processes to which they are subjected, especially temperature. The aim of the study was to compare the total content of polyphenols and antioxidant activity of chocolates obtained from roasted and unroasted cocoa beans. The chocolates produced from each of the six types of unroasted beans and each of the five types of roasted beans were investigated. The seeds came from Ghana, Venezuela, the Dominican Republic, Colombia and Ecuador. The highest total polyphenol content was determined in cocoa beans originating from Colombia and in the chocolates obtained from them. A higher content of total polyphenols was found in unroasted cocoa beans, which indicates the influence this process had on the studied size. The ability to scavenge free DPPH radicals was at a high level in both the beans and the chocolates produced from them, irrespective of the region where the raw material was grown. A positive correlation between the total polyphenol content and the ability to scavenge free radicals was found.
... The effect of the growing conditions on the cocoa beans was not strong in comparison to postharvest processes. 6,7,10,12,15,48 But it can explain the observed variations. Also the harvesting season showed an influence on the cocoa beans' chemical composition. ...
Article
Cocoa beans are produced all across the humid tropics under different environmental conditions provided by the region but also by the season and the type of production system. Agroforestry systems compared to monocultures buffer climate extremes and therefore provide less stressful environment for the understory cocoa, especially under seasonally varying conditions. We measured element concentration as well as abiotic stress indicators (polyamines and total phenolic content) in beans deriving from five different production systems comparing monocultures and agroforestry systems and from two harvesting seasons. Concentrations of N, Mg, S, Fe, Mn, Na and Zn were higher in beans produced in agroforestry systems with high stem density and leaf area index. In the dry season, the N, Fe and Cu concentration of the beans increased. The total phenolic content increased with proceeding of the dry season while other abiotic stress indicators like spermine decreased, implying an effect of the water availability on the chemical composition of the beans. Agroforestry systems did not buffer the variability of stress indicators over the seasons compared to monocultures. The effect of environmental growing conditions on bean chemical composition was not strong, but can contribute to variations in cocoa bean quality.
... One of the basic technological operation in cocoa bean processing affecting the quality of cocoa derivative products is roasting (Oracz & Nebesny, 2014). It determines the character of the chemical and physical processes that occurred inside the beans, and the final products quality (Wieslawa Krysiak & Motyl-Patelska, 2006). ...
Article
Full-text available
This study aimed to measure the effect of roasting time on physicochemical properties and volatile compounds of unfermented cocoa liquor roasted with an oil bath method. Physicochemical properties (pH, temperature, and color), flavor, and volatile compounds were analyzed. The results showed that the longer the roasting time the higher the unfermented cocoa liquor’s temperature, °Hue, and ΔE value, but lower pH and L value. There were 126 volatile compounds obtained by various roasting time, identified as pyrazines (12), aldehydes (16), esters (1), alcohols (31), acids (15), hydrocarbons (11), ketones (19), and others (21). At 15, 20, and 25 minutes of roasting time, 69, 74, and 67 volatile compounds, respectively, were identified. Volatile compounds’ profiles were indicated to be strongly influenced by roasting time. The largest area and highest number of compounds, such as pyrazines and aldehydes, were obtained at 20 minutes, which was also the only time the esters were identified. As well as the time showed a very strong flavor described by panelists.
... The increasing of biogenic amine level during roasting can be due to release of conjugated amines or chemical decarboxylation of amino acids in the presence of α-dicarbonyl compounds. The effect of air humidity on increasing biogenic amine concentration can be more effective heating of the cocoa beans compared to dry air (Oracz & Nebesny, 2014). In another study, there was a significant decrease in serotonin concentration of coffee beans after roasting at 300°C for 6 min whereas coffee beans had more serotonin content after 12 min of roasting compared to coffee beans roasted for 6 min (Cirilo et al., 2003). ...
... Different techniques have been applied for the analysis of such samples, for example High Performance Liquid Chromatography -Ultraviolet detection (HPLC-UV), or Nuclear Magnetic Resonance (NMR) spectroscopy (Caligiani et al., 2014;Natsume et al., 2000). However, Ultra Performance Liquid Chromatography-High Resolution Mass Spectrometry (UPLC-HRMS) is the preferred technique when analyzing also minor non-volatile constituents, (like biogenic amines, as reported by Oracz and Nebesny (2014)) and is applied in this research. With regard to the volatile compounds, different extraction procedures combined with various analytical techniques were already tested (Counet, Callemien, Ouwerx, & Collin, 2002;Frauendorfer & Schieberle, 2008;Owusu, Petersen, & Heimdal, 2011). ...
Article
Cocoa products are obtained from the seeds of Theobroma cacao L. In this research, cocoa liquor and chocolate produced from cocoa beans from West Africa (Forastero, "bulk" cacao) and Ecuador (Nacional variety, "fine-flavor" cacao), were investigated, using a novel approach in which various analytical techniques are combined in order to obtain in-depth knowledge of the studied cocoa samples. The levels of various classes of primary metabolites were determined and a wide range of secondary metabolites, including volatile organic acids, aldehydes, esters, pyrazines, polyphenols, methylxanthines and biogenic amines, were identified and/or quantified by HS-SPME GC-MS (headspace-solid phase microextraction gas chromatography - mass spectrometry). and UPLC-HRMS (ultra-performance liquid chromatography - high resolution mass spectrometry). Odor Activity Values (OAV) were calculated to assess the contribution of individual volatiles on the final aroma. Various volatile aroma compounds were more abundant in the West African cocoa liquor and chocolate, while the Ecuadorian samples were richer in most quantified non-volatile metabolites. Principal component analysis (PCA) confirmed that the four samples can be clearly distinguished. Alcohols, pyrazines, amino acids and biogenic amines were found to be highly influential in causing this differentiation. The proposed approach can be useful in future studies on more extensive cocoa sample collections, in order to highlight similarities and pinpoint typical differences in chemical composition among these samples.
... During cocoa roasting, increased levels of phenylethylamine, tyramine, tryptamine, dopamine, and serotonin were observed and the increase correlated positively with temperature (110 CÀ150 C) and air humidity (0.3%À5.0%). There can also be loss of some amines (putrescine and cadaverine) due to volatilization (Gloria and Engeseth, 2019a,b;Oracz and Nebesny, 2014;Özdestan, 2014;Restuccia et al., 2015). p0610 During germination, there can be formation of biogenic amines due to the physiological changes in the tissues. ...
Chapter
Since the early 1960s, a series of potentially mutagenic and carcinogenic xenobiotics have been identified in foods, resulting from chemical changes induced by processing. The toxic effects have been extensively studied and demonstrated in experimental animals and human cells and tissues; human clinical and epidemiological studies, however, are lacking. Chapter 10 features eight types of such potentially harmful substances (i.e., acrylamide, benzene, biogenic amines, ethyl carbamate, furan and methylfurans, heterocyclic aromatic amines, 3–MCPD and 3–MCPD esters, and nitrosamines). For each one, their chemical structures, occurrence in foods, mechanisms of formation, influencing factors, mitigating strategies, and toxicological aspects are discussed. With the exception of certain biogenic amines, which have some health benefits, and furan, which contributes to the typical aroma of certain foodstuffs (e,g., roasted coffee), substances herein addressed are known for their possible detrimental effects on health. Efforts have been made to minimize their formation, principally by improving the processing and home preparation methods. However, care should be taken that mitigation strategies do not undermine microbial safety and desirable sensory properties.
... These amino acids can then be enzymatically decarboxylated by some microorganisms forming amines (Granvogl et al., 2006). The low pH value favours the decarboxylase activity during fermentation, associated with a defence mechanism developed by microorganisms to protect themselves from acidic environments (Gloria et al., 2005;Oracz and Nebesny, 2014). Biogenic amines, even at low levels, are relevant to human health, while some of them can cause adverse effects at high levels. ...
Article
In this work, we determined the degree of filamentous fungi contamination in cocoa fermented seeds and the fungal potential to produce enzymes that could contribute to the cocoa quality. Internal transcribed spacer amplicon sequencing (ITS) showed 11 different species with Byssochlamys spectabilis, Aspergillus niger, Aspergillus flavus, Aspergillus carbonarius, Circinella muscae and Penicillium citrinum as the most abundant species. Our results evidenced intra and inter-species differences in the enzymes production. Cellulases, β-glucosidase, ornithine decarboxylase and phenylalanine decarboxylase were the most diffused enzymes expressed in the 53 strains here studied. Moreover, A. niger (6/12), A. carbonarius (2/3), and P. citrinum (3/3) showed high pectinolytic activity. Remarkable was the amino decarboxylase activity of P. citrinum, and A. flavus strains. For the first time we reported the presence of B. spectabilis in cocoa fermented beans, which could play an important role in the biogenic amines formation. In addition, we explored the capability of the Aspergillus section Nigri strains, to produce ochratoxin A (OTA) in a cacao model system (CPMS) and in malt extract medium (MEL). We observed that CPMS, but not MEL, stimulated the OTA production in 6 out 15 strains of Aspergillus section Nigri, reaching values ranging between 1.70 and 4995 μg OTA kg⁻¹ dry mycelium.
... It is desirable to optimize roasting conditions that maximize the desired compounds' production while preserving a desirable sensory profile. Nevertheless, roasting increases the content of biogenic amines (entry 7), resulting in Trinitario beans the highest final content [104]. The main biogenic amines found are 2-phenylethylamine, Fig. 6 Illustrative diagram of the stages of roasting cocoa in a roaster tyramine, tryptamine, serotonin, dopamine, and histamine [78,105]. ...
Article
Full-text available
The quality of cocoa depends on both the origin of the cacao and the processing stages. The roasting process is critical because it develops the aroma and flavor, changing the beans’ chemical composition significantly by chemical reactions induced by thermal energy. Aspects have been identified as the main differences between bulk cocoa and fine cocoa, the effect of time and temperature on the formation of the flavor and aroma, and the differences between conductive heating in an oven, convective with airflow, and steam flow. Thermal energy initially causes drying, then non-enzymatic browning chemical reactions (Maillard reaction, Strecker degradation, oxidation of lipids, and polyphenols), which produce volatile and non-volatile chemical compounds related to the flavor and aroma of cocoa roasted. This review identified that the effect of the heating rate on the physicochemical conversion of cocoa is still unknown, and the process has not been evaluated in inert atmospheres, which could drastically influence the avoidance of oxidation reactions. The effect of particle size on the performance of product quality is still unknown. A more in-depth explanation of energy, mass, and chemical kinetic transfer phenomena in roasting is needed to allow a deep understanding of the effect of process parameters. In order to achieve the above challenges, experimentation and modeling under kinetic control (small-scale) are proposed to allow the evaluation of the effects of the process parameters and the development of new roasting technologies in favor of product quality. Therefore, this work seeks to encourage scientists to work under a non-traditional scheme and generate new knowledge.
... Criollo, Trinitario, and Nacional are however defined as highquality ("fine" grade) varieties, Ecuador being the main producer worldwide of "fine" cocoa beans (Afoakwa et al. 2008;Dand 2011a; Exporters-Ecuador National Association of Cocoa 2016; Kongor et al. 2016;Vargas Jentzsch et al. 2016;International Cocoa Organization 2017). Contrary to other varieties, Nacional has a very short fermentation time and yields excellent beans in terms of flavour (Afoakwa et al. 2008;Motamayor et al. 2008;Afoakwa et al. 2011;Dand 2011b;Oracz and Nebesny 2014;Kongor et al. 2016). Pure Nacional cocoa genotypes are currently scarce and most of the orchards use natural hybrids introduced from Trinidad and Venezuela, which forms the Nacional and Trinitario complex (also known as "Arriba" cocoa). ...
Article
Full-text available
Cocoa presents a high fat content and a unique fatty acid profile defining its technological and nutritional properties. This study evaluated the fat content and fatty acid composition of Nacional cocoas, a worldwide recognised "fine" variety, collected in 85 Ecuadorian farms while taking into account 3 geographical levels (region, province, and canton). The total fat content varied from 45.61 ± 1.27 to 52.13 ± 0.58 g/100 g DW and was higher in the provinces and cantons from the Amazonian region than in those from the Pacific Coast region. A remarkable effect of the region and the province was shown on the content of individual fatty acids of Nacional cocoa beans. Total amounts of saturated and unsaturated fatty acids also depended on the growing area. Multivariate analysis provided a comprehensive assessment of the cocoa fat composition according to the origin, which may be useful for the selection of cocoas with specific technological and nutritional characteristics. ARTICLE HISTORY
... Elevated peak intensity was observed in 1000-800 cm À1 region in defined treatments of this study, which is usually attributed to R-NH 2 of primary amines. The effect of temperature and time of roasting on amines was also studied by Oracz and Nebesny (2014). During roasting, the amount of biogenic amines increases due to oxidative decarboxylation of parent amino acids and release of conjugated amines in the presence of a-dicarbonyl compounds or lipid peroxidation products (developed due to high temperature). ...
Article
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The effect of roasting on the physical, color, thermal, functional and antioxidant properties of chickpea was investigated. Chickpea grains were roasted in sand at three temperatures (180, 200 and 220°C) for different times (5, 10 and 15min). Highest surface area and lowest bulk density was obtained for grains roasted at 220°C for 15min. The lightness ‘L’ of flour decreased from 88.48 (unroasted) to 78.73 (220°C, 15min) while significant increase in ‘a’ and ‘b’ color values was observed from -0.73 to 2.25 and 22.43-24.83, respectively on roasting. Significant decrease in enthalpy of gelatinization (-0.14 to -0.46J/g), enthalpy of amylase-lipid complex (4329-2293J/g), total flavonoid content (22.89-16.64mg quercetin equivalents/100g) and antioxidant activity (22.85 to 7.36%) was observed upon roasting. However, roasting led to an increase in water absorption capacity (0.89-3.64g/g), water absorption index (1.97-3.52) and oil absorption capacity (1.60-3.54g/g).
... Fermented meat products, such as fermented sausages, attain the highest β-phenylethylamine concentrations (up to 182 mg/kg), with fish and fish products (up to 180 mg/kg), fish sauces (up to 172 mg/kg) close behind. This BA is also found in fermented dairy products, such as cheese (up to 61 mg/kg) [European Food Safety Authority (EFSA), 2011], in alcoholic beverages such as beer (up to 8.4 mg/kg), and in vegetables and vegetable products (up to 9.3 mg/kg) [European Food Safety Authority (EFSA), 2011] including cocoa beans and cocoa-containing foods such as chocolate (Oracz & Nebesny, 2014). The β-phenylethylamine present in cocoa-containing foods is, however, usually the result of thermal processing rather than microbial decarboxylation (Irsfeld, Spadafore, & Pruss, 2013). ...
Article
β-phenylethylamine and tryptamine are biogenic amines (BA) often found in foods. In general, BA are assumed to be toxic and their accumulation in food is not recommended. However, present knowledge regarding the toxicity of β-phenylethylamine and tryptamine is limited; more information is needed if qualitative and quantitative risk assessments of foods are to be successfully conducted. This study describes a real-time analysis of β-phenylethylamine and tryptamine toxicity on a human intestinal epithelial cell line. Both BA caused cell necrosis and apoptosis, although the former was the main mode of action of β-phenylethylamine, and the latter the main mode of action of tryptamine. Only tryptamine was cytotoxic at concentrations found in BA-rich foods. The results presented in this work may contribute to establish legal limits for β-phenylethylamine and tryptamine in food.
... A roasting treatment at 130°C for 30 min did not significantly affect the concentration of L-tyrosine and L-α-phenylalanine was reduced with 18%, compared to the non-roasted sample. Furthermore, the present study revealed a similar decreasing trend for tryptophan, with only significant lower (p < 0.05) levels measured for the intensive roasted samples at 130°C for 50 min and at 160°C for 30 min, presumably caused by oxidation and decarboxylation (Oracz & Nebesny, 2014). A diminution of 5-hydroxy-DL-tryptophan (5-HTP) during roasting could be expected, as this compound can degrade to serotonin after thermal decarboxylation; moreover, it is sensitive to oxidation (Martins & Gloria, 2010). ...
Article
The mood pyramid of cocoa, which was previously proposed as a new concept, consists of four levels (flavan-3-ols, methylxanthines, minor compounds and orosensory properties). Roasting is a crucial process for flavor development in cocoa but is likely to have a negative impact on the phytochemicals. We investigated the effect of roasting time (10 – 50 min) and temperature (110 – 160 °C) on the potential mood-enhancing compounds corresponding to the distinct mood pyramid levels. Phytochemicals were analyzed using UPLC-HRMS, while the flavor was mapped via aroma (HS-SPME-GC-MS) and generic descriptive analysis (trained panel). Results revealed that roasting at 130 °C for 30 min did not significantly affect the levels of epicatechin, procyanidin B2 and theobromine, while salsolinol significantly increased. Moreover, bitterness and astringency were reduced and the desired cocoa flavor was developed. Thus, through selection of appropriate roasting time and temperature conditions phytochemicals of interest could be retained without comprising the flavor.
... For obtaining chocolate from cocoa beans, one very important stage in the process is the roasting [4], which results in the production of desirable flavor and aroma compounds, as well as color changes [5]. The temperature and duration of roasting substantially affected the character in chemical and physical changes of cocoa beans [6]. ...
Article
Full-text available
Cocoa beans are the main raw material for the manufacture of chocolate and are currentlygaining great importance due to their antioxidant potential attributed to the total phenolic content(TPC) and the monomeric flavan-3-ols (epicatechin and catechin). The objective of this study was todetermine the degradation kinetics parameters of TPC, epicatechin, and catechin during the roastingprocess of Criollo cocoa for 10, 20, 30, 40, and 50 min at 90, 110, 130, 150, 170, 190, and 200◦C. Theresults showed a lower degradation of TPC (10.98±6.04%) and epicatechin (8.05±3.01%) at 130◦Cand 10 min of roasting, while a total degradation of epicatechin and a 92.29±0.06% degradationof TPC was obtained at 200◦C and 50 min. Reaction rate constant (k) and activation energy (Ea)were 0.02–0.10 min−1and 24.03 J/mol for TPC and 0.02–0.13 min−1and 22.51 J/mol for epicatechin,respectively. Degradation kinetics of TPC and epicatechin showed first-order reactions, while thecatechin showed patterns of formation and degradation
Article
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This study investigated the profile of cacao beans from the local Cameroonian Trinitario (SNK) and Forastero (TIKO) in terms of aroma precursors (amino acids and reducing sugars) through fermentation like incubations. Treatments consisted of incubating beans in acetic acid, 100 mmol/L for two days followed by 200 mmol/L of acetic acid for three days (Treatment T1) and in 100 mmol/L of lactic acid for two days followed by 200 mmol/L of acetic acid for three days (Treatment T2). Both treatments resulted in an increase of free amino acids content by 1.5-2.5 times in SNK and TIKO varieties. The ratio of the hydrophobic amino acids over the rest of amino acids showed the preponderance of T1 on the hydrophobic amino acids released in TIKO while in the SNK, some varieties displayed the highest ratio in T2. Glucose and fructose content in TIKO and SNK beans increased 2 to 3 times during incubation. Galactose and raf-finose were found in unfermented beans. After incubation, raffinose was missing while at the same time a raise of galactose content could be seen. These results highlighted that acidification remains the factor inducing the releasing of free hydrophobic amino acids, the genotype being less involved.
Article
The cocoa varieties Criollo, Forastero and Trinitario, which have different organoleptic properties, quite often are mixed together in cocoa-based products. The objective of this work was to develop a rapid method for the simultaneous determination of polyphenols (n = 35) and alkaloids (n = 2) in cocoa-based products by using the high throughput advantages provided by the Q Exactive Hybrid Quadrupole-Orbitrap Mass Spectrometer (HRMS). The proposed procedure was optimized and validated in terms of selectivity and specificity (mass accuracy <5 ppm), sensitivity (instrumental limit of detection from 15 to 30 fg), linearity (r² > 0.990), accuracy (recovery range from 89.1 to 112.4%) and precision (relative standard deviation <10%). The method was applied to 80 cocoa-based samples. Alkaloids represented on average the 57.7% of assayed compounds. Flavanols and procyanidins were the most abundant polyphenols being quantified in a range between 261 and 668 mg/kg and from 127 to 405 mg/g, respectively. Mass equivalents but structural isomers bioflavonoids were characterized by using the HRMS-Orbitrap methodology here developed.
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Roasting of chickpea is an important step for the development of value added product, performed normally at 150–350 °C using conduction, convection and radiation. In this study, continuous roasting of chickpea grains was performed without incorporating sand and using a novel method. The roasting characteristics, physico-functional and antioxidant properties of products obtained through this method at 250, 270, 290, 310, 330 and 350 °C were compared to unroasted grain. The results showed that grains roasted at 350 °C possessed highest puffing index, high expansion index and lowest length/width ratio. Color of roasted chickpea flour changed from light to dark with a simultaneous increase in ‘a’ and ‘b’ value. Functional properties in terms of water absorption index and oil absorption capacity were between 1.97-2.99 and 1.25–1.81 g/g respectively. Total flavonoid content of chickpea decreased by 10% while an increase occurred in total phenolic content (46%) and antioxidant activity (60%) respectively. FTIR and DSC profiles of roasted grain flour indicated changes in different functional groups and crystalline nature of starch. This method demonstrated that chickpea may be roasted effectively without any contamination in lesser time compare to other processes. Novel continuous roasting therefore could be considered for chickpea roasting industry.
Chapter
Commercially prepared acid-catalysed solutions are neutralized when the desired level of inversion is reached. Neutralization, however, needs to be done carefully; if the pH exceeds 7, the colour of the solution rapidly becomes brown because of the development of so-called reversion products. According to the Arrhenius law, acidic inversion is catalysed by temperature rise. In the confectionery industry, the concept of caramelization is applied in two different ways: the Maillard reaction (non-enzymatic browning) and sugar melting. The Maillard reaction is not the only non-enzymatic browning reaction. The caramelization reaction is in many ways similar to the Maillard reaction, except that only sugar compounds take part in the caramelization process. While inversion and caramelization are technologically useful chemical processes to a certain limited extent, acrylamide formation during food technology seems unambiguously to be detrimental to health.
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The impact of microwave roasting cocoa beans on the aroma and phytochemical profile of dark chocolates (70% cocoa) was studied. Three chocolates produced from microwave roasted beans (450 W–55 min, 600 W–35 min, 900 W–20 min) were compared with a chocolate produced from convectively roasted beans (130 °C–30 min). Aroma analysis via HS-SPME-GC-MS indicated that microwave roasting of cocoa beans resulted in chocolate with a distinctive aroma profile, compared to the chocolate produced from convectively roasted beans. Increased power input seems the main inducer of elevated levels of aroma compounds. Interestingly, the impact of the four treatments on the phytochemical profile, measured via LC-HRMS, of the chocolates was rather limited. Microwave roasting of cocoa beans was more prone to oxidation, but still within acceptable limits. The results validate that microwave roasting is a promising alternative technique that can be used effectively for chocolate production.
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La presente investigación tuvo como objetivo comparar el perfil sensorial de muestras de cacao de varias zonas productoras del país. Con este propósito el Laboratorio de Calidad Integral de Cacao y Chocolate de la Estación Experimental Tropical Pichilingue del INIAP, recibió muestras de 11 asociaciones de productores. Un panel de cinco miembros con experiencia en degustación de pasta de cacao (licor) produjo datos para los siguientes componentes del sabor: cacao, acidez, amargor, astringencia, caramelo, floral, frutal, nuez y verde. El análisis comparativo de las muestras se llevó a cabo mediante la prueba no paramétrica de Kruskal & Wallis. El grado de asociación de distintos pares de variables se examinó mediante un análisis correlacional. La relación entre muestras también se exploró mediante el análisis multivariado de componentes principales. Este análisis condujo a la identificación de las variables originales que más aportaron a la varianza de los dos primeros componentes principales. Diferencias estadísticamente significativas entre muestras se detectaron solo para el sabor a cacao. Las correlaciónes más altas se dieron entre las variables frutal y verde, frutal y astringencia, frutal y amargor, y frutal y nuez, la mayoría de signo negativo. Las variables con más aportación a la varianza (35.20%) del primer componente principal fueron frutal, verde y amargor. Acidez, floral y nuez hicieron la mayor aportación al segundo componente principal. La aparente estructuración de dos grupos muestrales en el plano definido sugiere semejanzas y diferencias en su perfil sensorial.
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Composition of cocoa beans depends on origin and cocoa processing such as fermentation, drying and roasting. However, less research has been conducted to analyse the composition of Peninsular Malaysia cocoa bean at different processing stages. Thus, the purpose of this study was to determine the proximate, phytosterol level, antioxidant content and activity of Peninsular Malaysia unfermented, unroasted, roasted cocoa beans and cocoa shells. Analysis involved was proximate analysis, total phenolic compound (Folin–Ciocalteu reagent assay), antioxidant activity (2,2-diphenyl-1-picrylhydrazyl scavenging assay) and phytosterol composition. Results show that the crude fiber of unroasted cocoa beans and cocoa shells increased from 17.19 to 28.45% and 13.86 to 16.06% respectively after roasting process. The roasting process is suspected to increase the dietary fiber content of cocoa products due to the interaction between polysaccharides, protein, polyphenolic and Maillard products at high temperature. The total phenolic content in cocoa bean and cocoa shells ranged from 2.42 to 10.82 µg GAE/ml. The unfermented cocoa beans contain significantly (p < 0.05) higher antioxidant activity (92.3%) compared to other samples. This study shows that cholesterol, stigmasterol and β-sitosterol were present in roasted cocoa beans and cocoa shells. Hence, the information on the composition of Malaysia unfermented, unroasted, roasted cocoa beans and cocoa shells are needed to enrich the databases composition as a reference for the cocoa industry. © 2018 Springer Science+Business Media, LLC, part of Springer Nature
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There is burgeoning interest among the supramolecular chemists to develop novel molecular systems to detect biogenic amines and bio-thiols in aqueous and non-aqueous medium due to their potential role in the biological processes. Biogenic amines are a biologically important target because of their involvement in energy metabolism of human biological systems and its requirement is met through food and nutrition. However, the increasing stances of serious health problems due to food toxicity have raised the quality of foods nowadays. Biogenic amines have been frequently considered as the markers or primary quality parameters of foods like antioxidant properties, freshness and spoilage. For instance, these amines such as spermine, spermidine and cadavarine etc. may originate during microbial decarboxylation of amino acids of fermented foods/beverages. These amines may also react with nitrite available in certain meat products and concomitantly produce carcinogenic nitrosamine compounds. On the other hand, it is also well established that the biothiols, particularly, thiol amino acids provides the basic character to food including flavor, color and texture that determine its acceptability. For instance, the reduction of thiol groups produces hydrogen sulfide which reduces flavour as in rotten eggs and spoiled fish, and the presence of hydrogen sulfide in fish is indicative of spoilage. Thus, biogenic amines and bio-thiols have attracted the profound interest of researchers as analytical tools for their quantification. Much scientific and technological information is issued every year, where the establishment of precise interactions of biogenic amines and bio-thiols with other molecules is sought in aqueous and non-aqueous medium. This review summarizes the optical chemosensors developed for the selective detection of biogenic amines and bio-thiols.
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La presente investigación tuvo como objetivo comparar el perfil sensorial de muestras de cacao de varias zonas productoras del país. Con este propósito el Laboratorio de Calidad Integral de Cacao y Chocolate de la Estación Experimental Tropical Pichilingue del INIAP, recibió muestras de 11 asociaciones de productores. Un panel de cinco miembros con experiencia en degustación de pasta de cacao (licor) produjo datos para los siguientes componentes del sabor: cacao, acidez, amargor, astringencia, caramelo, floral, frutal, nuez y verde. El análisis comparativo de las muestras se llevó a cabo mediante la prueba no paramétrica de Kruskal & Wallis. El grado de asociación de distintos pares de variables se examinó mediante un análisis correlacional. La relación entre muestras también se exploró mediante el análisis multivariado de componentes principales. Este análisis condujo a la identificación de las variables originales que más aportaron a la varianza de los dos primeros componentes principales. Diferencias estadísticamente significativas entre muestras se detectaron solo para el sabor a cacao. Las correlaciónes más altas se dieron entre las variables frutal y verde, frutal y astringencia, frutal y amargor, y frutal y nuez, la mayoría de signo negativo. Las variables con más aportación a la varianza (35.20%) del primer componente principal fueron frutal, verde y amargor. Acidez, floral y nuez hicieron la mayor aportación al segundo componente principal. La aparente estructuración de dos grupos muestrales en el plano definido sugiere semejanzas y diferencias en su perfil sensorial.
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This work analyzed the effect of infrared roasting at 100, 150, and 200°C on the main physical and chemical changes of cocoa. Raw and roasted cocoa were analyzed using Brunauer–Emmett–Teller, Fourier transform infrared spectroscopy, modulated differential scanning calorimetry (MDSC), thermogravimetric analysis (TGA), SPME, and GC‐MS. Using MDSC, the fusion of fat at around 35°C, and the desolvation of water and volatile compounds were identified. TGA detected loss of mass of various groups of chemical compounds, including those present pre‐roasting and generated during roasting. The unroasted cocoa's total sugar content of 2.71% decreased to 0.64% when roasted at 200°C, whereas roasting at 200°C generated seven (7) pyrazines. Tetramethylpyrazine is the most abundant, reaching the highest concentration when roasted at 150°C, but decreases when roasted at 200°C, due to the high temperature. To obtain the maximum production of favorable pyrazines, the temperature must be controlled based on the quality objectives of the final product. Practical applications The process of roasting cocoa is of great importance to the chocolate and derivatives industry. Knowledge of the chemical and physical changes that occur during roasting can help to optimize the operating conditions to obtain a better‐quality product, in particular by conserving and developing the flavor and aroma of fine Criollo cocoa varieties. This will support the industrialization of fine cocoas, presenting an option for improving the economic and social development of marginalized countries and communities.
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Rapid and real-time monitoring of food quality plays critical roles in the food industry and for the general public health. Herein, we specially synthesized a new perylene bisimide (PBI) derivative (PCB-EpE) composed of two PBI units and a rigid o-carborane linker, which was further employed in constructing a conceptual fluorescent film sensor for evaluating fish freshness. Photophysical studies indicate that PCB-EpE displays an open “Z-type” molecular configuration in chloroform and a closed “Δ-type” configuration in methyl cyclohexane. Comparatively, “Z-type” molecular configuration possesses higher fluorescence quantum yield and is more sensitive toward volatile basic nitrogen (VBN). It is noteworthy that the film sensor responds in less than 1 s even in ambient humidity condition. High correlation between the content of total volatile basic nitrogen (TVB-N) in evaluating fish freshness with different storage time and the fluorescence response is achieved. Detection limit of the film sensor toward trimethylamine as an example is lower than 1.0 ppm. Comprehensive sensing investigations demonstrate the rapid detection, strong anti-interference capability and excellent reusability of the film sensor toward testing VBN. To our knowledge, this is the first report to accurately predict TVB-N value for the evaluation of fish freshness using a fluorescent film sensor, showing great potential for real-life applications. This article is protected by copyright. All rights reserved.
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This study analyses the biogenic amines (BAs) formed in mackerel cooked by various methods and conditions. Five BAs, including tryptamine, β-phenylethylamine, putrescine, histamine, and spermidine, were analysed by high-performance liquid chromatography with UV detection. The level of total BAs was higher in the mackerel fillet (108.14 µg/g) than the headed and gutted fish (91.58 µg/g). Roasted, fried, and stewed mackerel recorded total BA concentrations of 54.28, 82.25, and 163.05 µg/g, respectively. Stewed mackerel contained about 3-fold more BAs than roasted mackerel. The level of total BAs in mackerel increased significantly up to 190%, 236% and 152% as the roasting temperature increased, upon frying, and as stewing temperature increased, respectively (p < 0.05).
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Cocoa (Theobroma cacao L.) is widely cultivated in tropical countries. The cocoa beans are a popular ingredient of confectionery. Cocoa beans contain various chemicals that contribute to their bioactivity and nutritional properties. There has been increasing interest in developing cocoa beans for “healthy” food products. Cocoa beans have special combination of nutrients such as lipids, carbohydrates, proteins and other compounds of biological activities. The bioactive phytochemicals include methylxanthines, polyphenols, biogenic amines, melanoidins, isoprostanoids and oxalates. These phytochemicals of cocoa are related to various in vivo and in vitro biological activities such as antioxidation, anti-cancer, anti-microbial, anti-inflammation, anti-diabetes, cardiovascular protection, physical improvement, anti-photoaging, anti-depression and blood glucose regulation. The potential of bioactive compounds in cocoa remains to be maximized for food and nutritional applications. The current processing technology promotes the degradation of beneficial bioactive compounds, while maximizing the flavors and its precursors. It is not optimized for the utilization of cocoa beans for “healthy” product formulations. Modifications of the current processing line and non-conventional processing are needed to better preserve and utilize the beneficial bioactive compounds in cocoa beans.
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High content of biogenic amine (BA) in huangjiu could pose serious quality concerns. More than 71% of BA in huangjiu were carried over from seriflux (rice soaking wastewater), which were produced by some BA producing bacteria during rice soaking process. A BA non-producing strain, Lactobacillus plantarum JN01, was introduced to rice soaking process, which decreased BA content in seriflux by 93.8% by niche competition at bench scale. Recycling of seriflux inoculated with L. plantarum JN01 at pilot run scale for ten batches demonstrated that BA in seriflux and huangjiu were reduced by 78.4% and 87.7%, respectively. The safety of huangjiu was enormously improved without affecting on the profiles of flavor compounds. Our results demostrated that seriflux recycling technology could reduce 50% of water consumption and achieve “zero effluents” in rice soaking process, which might potentially be a “green technology” not only for huangjiu brewing industry, but also for other related traditional fermented food industries.
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Roasting is an important process that contribute to formation of flavour compounds in cocoa beans. Pyrazines, a by-product of Maillard reaction is one of the character impact compounds that contribute to unique cocoa flavour. Unfortunately during roasting, carcinogenic acrylamide are also produced through Maillard reaction. Therefore, this study was focussed on optimising the roasting conditions using Central Composite Design (CCD) to produce superior quality cocoa beans with high concentration of pyrazines and low concentration of acrylamide. The roasting conditions used were temperatures in the range of 110°C to 160°C and time ranging from 15 min to 40 min. Roasting conditions significantly (p<0.005) affect the concentration of pyrazines in cocoa beans. However, the RSM analysis shows that the concentration of acrylamide in the beans was not influenced by the roasting conditions. Statistical optimisation based on maximum pyrazines and minimum acrylamide at temperature of 116°C and a time of 23 min produced the desirable value of 0.73. Hence, the optimized roasting conditions were able to produce high quality cocoa beans.
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This study concerns the influence of turning and fermentation method on quality of raw cocoa. Fermentation trials were conducted in wooden box, plastic box and in heaps with or not turning. Cocoa fermented in boxes during 4 days without stirring presented pH values above 5.0 while cocoa fermented in heaps presented pH 4.92. For fermentation with turnings, beans treated in wooden box were less acidic than beans fermented in plastic box, which recorded pH 4.75. Cocoa issued from all fermentations methods lasted 5 days without mixing presented pH above 5. Cocoa fermented in plastic box with turnings became acidic w ith pH 4.73 w hile acidity disappeared in beans fermented in heaps. A similar trend was observed in the titratable acidity of the dried beans. Cocoa fermented during 4 days w ithout turnings presented a high percentage of purple beans nearly 40% whatever the method. Percentages of defective, slaty and mouldy beans were below 4% with or without turnings. Cocoa beans fermented with turnings recorded about 10% of defectives beans whatever the process. Percentage of purple beans decreased to about 12% for cocoa fermented in wooden box. Naturally, percentage of brown beans increased for cocoa fermented both in wooden box and in heaps. All the beans showed no sign insect damages, and negligible levels of internal molding whatever the turning and the methods of fermentation.
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The cocoa beans of the Ivory Coast variety were convectively and microwave roasted. The effects of roasting conditions on the principal physicochemical attributes (water and fat contents, total and volatile acidity) of roasted cocoa beans and the properties of fat extracted from this material (acidity, saponification index, iodine index, peroxide value, light refraction coefficient, polar fraction content, and Fatty Acid profile, absorbancy of 1 and 10% solution in hexane) were examined. The characteristics of roasted and raw cocoa beans and their lipid fractions were compared. Results of analyses showed that convective roasting for 35 min at 135°C, air flow rate 1.0mxs<sup>-1</sup> and relative humidity RH of 0.45% caused the least advanced changes in fat quality while microwave roasting promoted oxidation of lipids although the quality of roasted cocoa beans was the best. Granos de cacao de la variedad Costa de Marfil se han sometido a tostado mediante convección y microondas. Se ha estudiado el efecto de las condiciones de tostado sobre los atributos físico-químicos principales (contenido de agua y grasa, acidez total y volátil) del cacao en grano tostado y las propiedades de la grasa extraída de este material (Acidez, índice de saponificación, índice de peróxidos, índice de yodo, índice de refracción, contenido de fracción polar, perfil de ácidos grasos, absorbancia de una solución al 10% en hexano). Se han comparado las características de los granos de cacao tostados y crudos y sus fracciones lipídicas. Los resultados de los análisis mostraron que el tostado mediante convección durante 35 minutos a 135°C, con un caudal de aire de 1,0 m s-1 y HR de 0,45 causó los menores cambios en la calidad de grasa mientras que el tostado mediante microondas promovió en mayor medida la oxidación de los lípidos aunque la calidad de los granos de cacao tostado fue mejor.
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Chocolate and cocoa are extensively used in many cultures. Although their composition has been studied, the functional significance of the components has not been as well defined. There are indications that cocoa constituents exert beneficial effects on human health, and therefore cocoa and chocolate may be considered functional foods. The use of functional foods to modulate human health has gained greater significance in recent years, and chocolate is widely consumed throughout society. We performed an extensive review of literature in both animal and human systems with respect to composition, bioavailability, comparative analysis with other food products and, especially, implications for cardiovascular disease and the human immune system. Although chocolate contains a high amount of saturated fats, the two major fatty acids are palmitic and stearic acid, which appear to have fewer implications for progression of coronary artery disease than other saturated fatty acids. In addition, the implications of flavonoids and other polyphenols in chocolate as antioxidants are significant, and their ability to modulate the immune system may also be applicable to infection and neoplasia. In this review, we attempt to place these issues in perspective and to provide the reader with an extensive summary of the literature on chocolate and cocoa and their potential mechanisms of action with respect to human health.
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Thirty-two samples of commercially available Greek wines were analysed in order to determine the content of biogenic amines. The method involves pre-column dansylation of the amines and subsequent solid phase extraction (SPE) of the derivatives through C 18 car-tridges. For the analysis, RP-HPLC (reversed phase-high performance liquid chromatography) coupled with fluorimetric detection at excitation and emission wavelengths of 320 and 523 nm, respectively was used. All amines measured had recoveries over 85%. The high-est detection limit was for agmatine (0.18 mg l À1). Putrescine, cadaverine, histamine and isoamylamine are the most abundant amines in the samples analysed. The relative concentrations of biogenic amines expressed in mg l À1 had as follows: putrescine > histamine > iso-amylamine > ethylamine > methylamine > cadaverine = tyramine = agmatine = tryptamine. Higher amounts of biogenic amines were generally detected in wines, aged for long periods in barrels or in bottles. However, young wines contained lower amounts of these com-pounds as they were directly bottled after winemaking and have not undergone any further maturation processing. Moreover, less acid wines gave rise to higher histamine contents.
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Raw cocoa is the processed and traded form of the cocoa seed. Fresh seeds undergo fermentation and a drying process before they are prepared for transport and shipping. Depending on the local situation in the producer region the seeds are collected from big estates and are fermented and dried in big lots or they originate from small farmer's crop trees. In the subsequent transport and trading chain raw cocoas may be mixed and stored before they finally are sold and brought to the consumer countries. Local or regional variations in cocoa plant material, fermentation procedures and drying processes finally result in a typical traded good with respect to the amino acids, which form an important part of the flavour precursors. These free amino acids and their composition result from the fermentation procedure of fresh seeds. In the course of the fermentation specific cleavage of cocoa storage proteins delivers the amino acid patterns. In this study the variation of free amino acid amount and distribution of 108 commercially fermented and traded cocoa samples and two Theobroma grandiflorum (Willd. ex Spreng.) K. Schum samples were determined. This examination showed clearly, that content and distribution of free amino acids in raw cocoa from different origins vary greatly (5–25mgg−1 fatfree dry matter), in some cases country and even region-specific differences were apparent. It is important to notice typical, region-specific variations in the amounts and compositions of free amino acids.
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Dopamine is an endogenous catecholamine that modulates many functions including behavior, movement, nerve conduction, hormone synthesis and release, blood pressure, and ion fluxes. Dopamine receptors in the brain have been classically divided into D1 and D2 subtypes, based on pharmacological data. However, molecular biology techniques have identified many more dopamine receptor subtypes. Several of the receptors cloned from the brain correspond to the classically described D1 and D2 receptors. Several D1 receptor subtypes have been cloned (D1A, D1B, and D5) and are each coupled to the stimulation of adenylyl cyclase. The D2 receptor has two isoforms, a shorter form, composed of 415 amino acids, is termed the D2short receptor. The long form, called the D2long receptor, is composed of 444 amino acids; both are coupled to the inhibition of adenylyl cyclase. The D3 and D4 receptors are closely related to, but clearly distinct from, the D2 receptor. They have not yet been linked to adenylyl cyclase activity. Outside of the central nervous system, the peripheral dopamine receptors have been classified into the DA1 and DA2 subtypes, on the basis of synaptic localization. The pharmacological properties of DA1 receptors roughly approximate those of D1 and D5 receptors, whereas those of DA2 receptors approximate those of D2 receptors. A renal dopamine receptor with some pharmacological features of the D2 receptor but not linked to adenylyl cyclase has been described in the renal cortex and inner medulla. In the inner medulla, this D2-like receptor, termed DA2k, is linked to stimulation of prostaglandin E2 production, apparently due to stimulation of phospholipase A2. Of the cloned dopamine receptors, only the mRNA of the D3 receptor has been reported in the kidney. The DA1 receptor in the kidney is associated with renal vasodilation and an increase in electrolyte excretion. The DA1-related vasodilation and inhibition of electrolyte transport is mediated by cAMP. The role of renal DA2 receptors remains to be clarified. Although DA1 and DA2 receptors may act in concert to decrease transport in the renal proximal convoluted tubule, the overall function of DA2 receptors may be actually the opposite of those noted for DA1 receptors. Dopamine has been postulated to act as an intrarenal natriuretic hormone. Moreover, an aberrant renal dopaminergic system may play a role in the pathogenesis of some forms of hypertension. A decreased renal production of dopamine and/or a defective transduction of the dopamine signal is/are present in some animal models of experimental hypertension as well as in some forms of human essential hypertension.
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Studies were conducted to evaluate effects of pod storage (as a means of pulp pre-conditioning) and fermentation time on the fermentative quality and appearance of Ghanaian cocoa beans. The fermentative quality (cut test and fermentation index [FI]) and colour (L, a, b) of the cocoa beans were studied using standard methods. Increasing pod storage and fermentation time significantly (P<0.05) influenced the fermentative quality and appearance of the beans. Fermentation caused significant increases in FI at all periods of pod storage whilst increasing pod storage resulted in darker, yellower and less red beans. Cut test scores revealed that storage of pods for 7 and 14 days increased the percentage of brown beans by 15 and 38% respectively by the sixth day of fermentation. Thus, Ghanaian cocoa pods could be stored for up to 14 days prior to fermentation with optimum fermentative quality and desired colour attained after 4 days of fermentation.
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The decarboxylation of phenylalanine in the presence of methyl 13-hydroperoxyoctadeca-9,11-dienoate (LOOH), 2,4-decadienal (DD), 4,5-epoxy-2-decenal (ED), 4-hydroxy-2-nonenal (HN), and 4-oxo-2-nonenal (ON) was studied both to explore the potential of lipid oxidation products (LOP) to produce amino acid decarboxylation and to understand the reaction pathways responsible for this degradation. All assayed LOP were able to decarboxylate phenylalanine, but their reactivity decreased in the following order when the reaction was carried out under non-oxidative conditions: DD > ED ≈ LOOH > HN ≈ ON. The reaction pathway is proposed to take place by decarboxylation of the imine formed between the amino group of the amino acid and the carbonylic group of the oxidized lipid. This decarboxylation is facilitated due to the formation of a relatively stable azomethine ylide after the loss of carbon dioxide from a 5-oxazolidinone intermediate. The azomethine ylide would, finally, evolve into new conjugated imines, which are the origin of both β-phenylethylamine and phenylacetaldehyde, which was also detected in the reaction mixtures. The activation energy (Ea) for the phenylalanine decarboxylation in the presence of 2,4-decadienal was 54 kJ/mol. Although additional studies are needed to determine the contribution of the chemical pathways described in this study to the overall biogenic amine formation in foods, this study provides the chemical basis both to understand how biogenic amines can be produced chemically from amino acids in the presence of lipid-derived carbonyls and to propose potential inhibitors in this route.
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The types and levels of free bioactive amines in different corn products were determined. The amines were analyzed by ion pair-HPLC, post-column derivatization with o-phthalaldehyde and fluorimetric detection. Fresh sweet corn contained mainly spermidine followed by putrescine. Spermine, cadaverine, phenylethylamine, histamine and agmatine were also present at low levels. The profile and levels of amines changed significantly in canned and dried corn. Putrescine was the prevalent amine in canned corn whereas spermine was prevalent in dried corn. Germinated corn had significantly higher spermidine, spermine and putrescine levels. The embryo of the corn contained significantly higher spermine levels compared to the endosperm. These results indicate that corn is a good source of polyamines and that the different types of corn products available can be used to provide a profile of amines according to specific dietary need.
Summary 2-Phenylethylamine was extracted from cocoa nibs and chocolates and analysed by coupled gas chromatography-mass spectroscopy. The amine concentration increases in fermentation of cocoa and decreased during roasting and alkalization. Its concentration in chocolates is dependent on non-fat cocoa contents. Previously unreported aldimines were found in cocoa powders, which arise from the condensation of phenylethylamine and aldehydes. The main component of these products isN-phenylmethyl-N-phenylmethylene amine (CAS 3240-95-7).
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The levels of ten free bioactive amines, as well as pH and color characteristics, were determined in different types and brands of instant coffee. The amines were extracted with trichloroacetic acid and quantified by ion-pair HPLC, post-column derivatization with o-phthalaldehyde and fluorimetric detection. Overall, nine amines were detected: serotonin, cadaverine, tyramine, spermidine, putrescine, histamine, agmatine, phenyletylamine and spermine. Tryptamine was not detected in any sample. Tyramine was present in every sample, followed by cadaverine and serotonin. Total amine levels in the dry instant coffee varied from 0.28 to 2.76mg/100g. Overall, serotonin was present at higher levels followed by cadaverine, tyramine and spermidine. Significantly higher tyramine levels were found in decaffeinated coffee and higher cadaverine levels were detected in decaffeinated and organic coffee. The levels of amines varied among lots of the same brand and among brands. The color characteristics varied among types of instant coffee. The pH of the beverage varied from 4.86 to 5.15, with higher levels in decaffeinated coffee. There was significant positive correlation between pH and the levels of tyramine and agmatine. Investigations are needed to ascertain the impact of these amines on coffee flavor and on human health, and to determine the factors which affect amine formation and accumulation in instant coffee.
Article
Tetrahydro-beta -carbolines (TH beta Cs), potential neuroactive alkaloids, were found in chocolate and. cocoa. 6-Hydroxy-1-methyl-1,2,3,4-tetrahydro-beta -carboline (60HMTH betaC), 1,2,3,4-tetrahydro-beta -carboline-3-carboxylic acid (THCA), 1-methyl-1,2,3,4-tetrahydro-beta -carboline-3-carboxylic acid (MTCA) in both diastereoisomers (1S,3S and 1R,3S), and 1-methyl-1,2,3,4-tetrahydro-beta -carboline (MTH betaC), besides serotonin and tryptamine biogenic amines, were identified and quantified in dark chocolate, milk chocolate, cocoa, and chocolate-containing cereals by RP-HPLC-fluorescence and HPLC-MS. For each TH betaC, the concentration ranges were determined: 60HMTH betaC (0.16-3.92 mug/g), THCA (0.01-0.85 mug/g), 1S,3S-MTCA (0.35-2 mug/g), 1R,3S-MTCA (0.14-0.88 mug/g), and MTH betaC (nd-0.21 mug/g). The highest content was generally found in chocolates and cocoas, but cereals containing chocolate also showed an appreciable amount of TH beta Cs. The possible biological implications of this novel group of alkaloids in chocolate are discussed.
Article
A selective and sensitive ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-MS) method was developed for the simultaneous determination of ten biogenic amines (tryptamine, 2-phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine, adrenaline, dopamine and spermine) in a thymopolypeptides injection from the Chinese market for the first time. Biogenic amines (BAs) were pre-column derivatised by dansyl chloride after direct sample dilution. Dansylated amines were separated on an ACQUITY UPLC BEH Shield RP18 column (2.1mm×150mm I.D., 1.7μm) using a gradient elution. Quantification was done by monitoring fragment ions of each derivative under the MS mode of multiple reaction monitoring (MRM). A satisfactory result of method validation was obtained. The linearity ranged from 0.32 to 1182.9μg/L and the correlation coefficients (r) for all amines were above 0.99. The LOD ranged from 0.08μg/L for 2-phenylethylamine and tyramine to 8.00μg/L for adrenaline; the LOQ ranged from 0.32μg/L for 2-phenylethylamine to 12.12μg/L for dopamine. The recovery ranged from 75.8 to 110.3% after spiking standard solutions of BAs to a sample at three levels. The intra and inter-day precision RSD were 0.78-8.85% and 1.39-9.93% respectively. Eighty-four injections were analyzed by this method. Nine biogenic amines were found in them except adrenaline. Moreover, the relationship between the result of test for depressor substances and the content of BAs was statistically analyzed.
Article
Twenty-one Natto products currently distributed in Korea were analysed for biogenic amine contents and tested to determine physicochemical and bacterial contributions to biogenic amine formation. Among them, nine products (about 43%) had β-phenylethylamine or tyramine contents greater than the toxic dose (30mg/kg and 100mg/kg, respectively) of each amine, although no products showed total amounts of biogenic amines above the harmful level (1000mg/kg), which indicates that the amounts of biogenic amines in some Natto products are not within the safe level for human health. From four different Natto products, that contained noticeable levels of β-phenylethylamine and tyramine, 80 bacterial strains were isolated. All the strains were identified to be Bacillus subtilis and highly capable of producing β-phenylethylamine and tyramine. Therefore, it seems likely that the remarkable contents of β-phenylethylamine and tyramine in Natto predominantly resulted from the strains highly capable of producing those amines present in the food.
Article
The effect of roasting on the levels of amines in high and low quality coffee was investigated. Arabica green coffee samples previously classified by cup as soft (high quality) and rio (low quality) were roasted at 220 °C. Bean samples were collected every 4 min during roasting. HPLC analysis was carried out for detection and quantification of bioactive amines. Putrescine was the prevailing amine in both samples, followed by spermidine and spermine. Putrescine levels were significantly higher for the rio sample compared to the soft one. Also, both histamine and tryptamine were only present in the rio sample. There was a significant decrease in total amine content during roasting, with degradation of putrescine, spermine, histamine and tyramine taking place mostly during the drying stage. Degradation of spermidine occurred at a slower rate.
Article
a b s t r a c t The contents of protein and non-protein (free and protein-bound) tryptophan and of proteins in cocoa beans of various origin were determined. Protein concentrations varied from 11.8 g/100 g in beans from the Dominican Republic to 15.7 g/100 g in roasted beans from the Ivory Coast. The highest protein tryp-tophan content was found in cocoa beans from Ecuador. Madagascar beans had the highest value of free tryptophan and Echeandia the lowest (17.26 and 6.39 mg/100 g, respectively). Tryptophan was bound to water-soluble proteins as well as to proteins soluble in buffer solution (pH 8.9) and in 70% ethanol. In particular, Dominican Republic cocoa contained the highest amount of tryptophan bound to water-solu-ble proteins. Very little tryptophan was linked to proteins soluble in alkaline or ethanol solutions, and values ranged from 0.96 to 3.04 and from 0.24 to 1.21 mg/100 g of dry defatted cocoa sample, respectively.
Article
In this study, commercial Malaysian cocoa beans (SMC1A) were roasted in a forced airflow-drying oven for 20, 30, 40 and 50 min at 120, 130, 140, 150, 160 and 170C. The products were evaluated for flavor compounds and sensory evaluation (as dark chocolate). The volatile fraction was isolated using the combined steam distillation–extraction procedure and was identified by gas chromatography–mass spectrometry. A quantitative descriptive analysis was used to evaluate the flavor intensity of the chocolates using a 9-point rating scale for selected flavor attributes, namely astringency, bitter taste, sour taste, cocoa and burnt. Panelists were asked to smell and taste the sample against a standard chocolate. It was found that there were significant differences in flavor compounds between the different conditions of roasting. The main flavoring compounds identified composed of aliphatic and alicyclic groups such as alcohol and ester, and heterocyclic groups such as pyrazine and aldehyde. A total of 19 volatile major components were identified: nine pyrazines (2,5-dimethyl-, 2,3-dimethyl-, 2-ethyl-6-methyl-, trimethyl-, 3-ethyl-2,5-dimethyl-, tetramethyl-, 2-ethenyl-6-methyl- and 3,5-dimethyl-2-methylpyrazine); five aldehydes (5-methyl-2-phenyl-2-hexenal, benzaldehyde, benzalacetaldehyde and α-ethyliden-benzenacetaldehyde); one methyl ketone (2-nonanone); two alcohols (linalool and 2-heptanol); and two esters (4-ethylphenyl acetate and 2-phenylethyl acetate). Based on the flavor profile of the compounds identified, an optimum production of the major flavoring compounds such as pyrazine, aldehyde, ketone, alcohol and ester occurred at 160C for 30 min of roasting. Trimethylpyrazine and tetramethylpyrazine compounds together with 5-methyl-2-phenyl-2-hexanal were found to be good indicators for the evaluation of the roasting process. However, based on chocolate evaluation, the best roasting temperature was 150C for 30 min, which gave the lowest astringency and at the same time gave the lowest bitter taste and low level of sour and burnt tastes. At 150C roasting temperature, the desirable cocoa flavor was at its optimum. Correlation coefficients among certain volatile flavor and sensory characteristics of cocoa beans and dark chocolate were significant (P < 0.05).
Chapter
The effectiveness of different compounds in the generation of acrylamide (AA) from asparagine, was determined by reacting asparagine with mono-, diand polysaccharides, as well as four different oxo-compounds known to be involved in carbohydrate metabolism/degradation. Quantitation of AA formed either under aqueous conditions or in low water model systems revealed glucose and 2-oxopropionic acid as the most effective compounds in AA generation, when reacted in model systems with a low water content (about 1 mol-% yield). Interestingly, heating of asparagine in the presence of 2-oxopropionic acid generated quite high amounts of 3-aminopropionamide (3-APA), which itself effectively generated AA upon heating in aqueous solution, as well as in low water systems. Because this is the first report on amounts of 3-APA generated by Maillard-type reactions, the general role of 3-APA as key intermediate in AA formation is discussed in detail. In addition, first results on the development and application of an HPLC/fluorescence method for AA quantitation are presented.
Chapter
The effects of theobromine in man are underresearched, possibly owing to the assumption that it is behaviourally inert. Toxicology research in animals may appear to provide alarming results, but these cannot be extrapolated to humans for a number of reasons. Domestic animals and animals used for racing competitions need to be guarded from chocolate and cocoa-containing foods, including foods containing cocoa husks. Research ought to include caffeine as a comparative agent, and underlying mechanisms need to be further explored. Of all constituents proposed to play a role in our liking for chocolate, caffeine is the most convincing, though a role for theobromine cannot be ruled out. Most other substances are unlikely to exude a psychopharmacological effect owing to extremely low concentrations or the inability to reach the blood–brain barrier, whilst chocolate craving and addiction need to be explained by means of a culturally determined ambivalence towards chocolate. KeywordsChocolate-Cocoa-Comparative-Craving-Liking-Myths-Pharmacology-Psychology-Theobromine-Toxicology
Article
The levels of free and total tryptophan and of 5-hydroxytryptophan (5-HTP) were investigated in green and roasted grains and beverages of Coffea arabica L. (Arabica) and Coffea canephora Pierre var. robusta (Robusta). Grains were light, medium and dark roasted. Free and protein tryptophan were extracted before and after hydrolysis. The levels of tryptophan and 5-HTP were quantified simultaneously by ion-pair HPLC and fluorimetric detection after derivatisation with o-phthalaldehyde. Robusta green coffee had higher total and protein tryptophan, whereas Arabica had higher free tryptophan levels. 5-HTP was not detected in the samples before and after roasting. Free tryptophan was completely degraded during roasting. Roasting significantly affected protein tryptophan. The rate of loss was smaller in Arabica compared to Robusta at every roasting degree. A beverage prepared the Brazilian way with a medium-roasted coffee provided 1.4–2.5 mg tryptophan/50 ml cup.
Article
The profile and levels of bioactive amines in green and roasted coffee were investigated. Coffea arabica L., variety ‘catuaı́ vermelho’, was harvested in São Sebastião do Paraı́so, state of Minas Gerais, Brazil. The green coffee was roasted at two degrees—American and French (300 °C for 6 and 12 min, respectively). The samples were analysed for bioactive amines. Roasted samples were also analysed for moisture content, water activity and L∗a∗b∗ colour characteristics. Total amine levels in green coffee ranged from 3.03 to 4.44 mg/100 g. The predominant amines in green coffee were serotonin and putrescine, followed by spermidine and spermine. The degree of roasting did not affect moisture content or water activity of the coffee bean. Hue angle and saturation were higher for American than for French coffee. The profile and levels of bioactive amines in roasted coffee differed significantly from green coffee. The prevailing amine in roasted coffee was serotonin, followed by spermidine. Putrescine and spermine were not detected in roasted coffee. The presence of agmatine was detected in French roasted coffee. American roasted coffee had lower amine levels than French, which indicated that, the stronger the degree of roasting, the higher were the total levels of amines.
Article
A rapid ultra-performance liquid chromatographic (UPLC) method for the determination of biogenic amines (putrescine, cadaverine, spermidine, spermine, phenylethylamine, histamine, tyramine and tryptamine) in selected food samples is described. The eight biogenic amines, which are the most important to be determined in food samples, were derivatized with dansyl chloride prior to UPLC separation. The dansylated amines were separated on an Agilent Zorbax Eclipse XDB – C18 column (50 × 4.6 mm ID, 1.8 μm) using gradient elution with a binary system of acetonitrile–water, a flow rate of 1.0 ml/min and UV detection at 225 nm. The analysis is very fast, all amines are well resolved and are eluted from the column in less than 6 min. The average repeatability of the method ranged between 1.02% and 2.14%. Limits of detection (LODs) for considered amines ranged between 0.032 and 0.098 μg/l; calibration curves showed very good linearity (r = 0.9994–1.0000). The method was applied to the analysis of amines in pork, beef, chicken and fish meat, cheese and edible mushrooms.
Article
Recent trends in food marketing suggest that cocoa products, besides being favourite sweets among consumers, also present multiple-benefit foodstuffs, which are becoming objects of increased scientific research, mainly because of their interesting phytochemical composition. UV/VIS spectrophotometric and high-performance liquid chromatography (HPLC-PDA) methods were applied in order to compare the composition of polyphenols and methylxanthines in commercial cocoa products affected by different extraction solvents. Antioxidant capacity of water and methanol extracts was evaluated using DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) and FRAP (ferric reducing/antioxidant power) assays. The obtained results confirmed that the content of polyphenols and methylxanthines, as well as the antioxidant capacity of cocoa products depend on the content of their cocoa solids. Among the tested cocoa products, the highest content of bioactive compounds (polyphenols and methylxanthines) was determined in extracts of cocoa products with the highest content of cocoa solids (cocoa liquor, cocoa powder and dark chocolate with 88% cocoa solids), while the lowest content was determined in milk chocolate and cocoa bar extracts. The most abundant phenolic compound in cocoa extracts was (−)-epicatechin, while the most abundant methylxanthine was theobromine. In comparison with water, 70% methanol demonstrated higher efficiency for the extraction of the studied bioactive compounds from cocoa products.
Article
Almost 500 clones of wild cocoa trees (Theobroma cacao L.) grown from pods collected in 1987 from wild mother-trees in the Camopi and Tanpok river basins (southeastern French Guiana) have been distributed in around fifteen cocoa producing countries since 1988. The name of those clones always bears the GU prefix (for “Guyane”, i.e. French Guiana). All the germplasm of the same geographical origin present in the CIRAD collection at Paracou-Combi (Sinnamary, French Guiana), i.e. more than 1600 trees, has been abundantly studied for its morphological characterization, its agronomic assessment or its genetic diversity. Other assessment work, primarily on resistance to certain diseases, has been carried out by CIRAD in Montpellier, or in various countries by other organizations.In order to simplify the choice for breeders faced with a large number of GU clones and wishing to use some of them, an overview is presented here of the results obtained with this germplasm for various selection criteria such as productivity, the yield:vigour ratio (cropping efficiency), pod filling, bean size, resistance to pests and diseases, compatibility, sensory qualities, etc. The results obtained for resistance of this material to witches’ broom disease and black pod rot show a globally high level of resistance, making the GU germplasm a new and major potential source of resistance to those diseases. The same seems to apply for resistance to mirid damage. The yield levels achieved in French Guiana, along with cropping efficiency, are noteworthy in some families. The first results acquired reveal a substantial heterosis effect when GU clones are hybridized with other groups.Given their distribution in several countries, the known individual qualities and performance of some GU clones present at the Reading quarantine station (UK) are indicated. A selection of clones that are of interest or promising for incorporation in breeding programmes is provided for each criterion.
Article
A method for the analysis of serotonin (5-HT) and its precursors, 5-hydroxytryptophan (5-HTP) and l-tryptophan (TP) in chocolate samples by capillary liquid chromatography-mass spectrometry (cLC-MS) has been developed. Optimum chromatographic conditions were established by using a personalized multifactorial experimental design. Finally the cLC separation was achieved through a mixture of acetonitrile and 5mM ammonium formate at pH 4 (3:97, v/v) as mobile phase in gradient elution, setting the injection volume at 10 μL and using pure water as injection solvent for focusing purposes on the head of the capillary column. For extraction of targets in chocolate samples a new, fast and simple procedure based on the use of acidic extraction medium and sonication was developed. Working in selected ion mode (m/z 177 for 5-HT, m/z 205 for l-tryptophan and m/z 221 for 5-HTP) detection limits were between 0.01 and 0.11 μg g(-1) and linearity was in the concentration range of 0.5-25 μg g(-1). Recoveries higher than 76% with RSDs lower than 8% were obtained from spiked samples for all analytes, showing the effectiveness of the proposed method. Serotonin and its precursors were determined in 5 kinds of commonly consumed chocolates with different cocoa contents (70-100%). The highest serotonin content was found in chocolate with a cocoa content of 85% (2.93 μg g(-1)). Regarding l-tryptophan, the highest content of this amino acid (13.27-13.34 μg g(-1)) was found in chocolate samples with the lowest cocoa content (70-85%). 5-Hydroxytryptophan was not detected in any chocolate samples.
Article
The effects of theobromine in man are underresearched, possibly owing to the assumption that it is behaviourally inert. Toxicology research in animals may appear to provide alarming results, but these cannot be extrapolated to humans for a number of reasons. Domestic animals and animals used for racing competitions need to be guarded from chocolate and cocoa-containing foods, including foods containing cocoa husks. Research ought to include caffeine as a comparative agent, and underlying mechanisms need to be further explored. Of all constituents proposed to play a role in our liking for chocolate, caffeine is the most convincing, though a role for theobromine cannot be ruled out. Most other substances are unlikely to exude a psychopharmacological effect owing to extremely low concentrations or the inability to reach the blood-brain barrier, whilst chocolate craving and addiction need to be explained by means of a culturally determined ambivalence towards chocolate.